A coating composition and articles made therefrom

ABSTRACT

The present disclosure includes a waterborne polyolefin based coating layer that has improved features as compared to epoxy coatings. The coating composition of the present disclosure include 40 to 80 weight percent (wt. %) of a base polymer; 10 to 30 wt. % of a polymeric stabilizing agent; 5 to 15 wt. % of a polymeric coupling agent; 0 to 35 wt. % of a polymeric performance improving agent; a neutralizing agent that partially or fully neutralize the polymeric stabilizing agent; and a fluid medium, where the wt. % values are based on the total weight of the base polymer, the polymeric coupling agent, the polymeric stabilizing agent and, when present, the polymeric performance improving agent (as used herein, this total weight of the base polymer, the polymeric coup ling agent, the polymeric stabilizing agent and, when present, the polymeric performance improving agent may be referred to as the “solid content” of the coating composition).

FIELD OF INVENTION

The instant invention relates to a coating composition and articles madetherefrom.

BACKGROUND OF THE INVENTION

The application of various treatment and pretreatment solutions tometals to retard or inhibit corrosion is well established. This isparticularly true in the area of metal food and beverage cans as well asnon-food metal containers. Coatings are applied to the interior of suchcontainers to prevent the contents from contacting the metal parts ofthe container. Contact between the metal and the food or beverage aswell as non-food substances can lead to corrosion of the metalcontainer, which can then contaminate the food or beverage or thenon-food contents of such metal containers. Corrosion is particularlyproblematic when food and beverage products are highly acidic natureand/or are having a high salt content such as a rhubarb-based productsor isotonic drinks. Also strong alkaline contents of non-food substancessuch as hair-dye may react with metal, for example, aluminum, parts ofcontainers. The coatings applied, for example, to the interior of foodand beverage cans also helps prevent corrosion in the head space of thecans, which is the area between the fill line of the food product andthe can lid. The coatings may be applied to the outside of metalcontainers to provide protection against the external environment or toprovide a decorative layer including fillers and/or pigments. Inaddition to corrosion protection, coatings for food and beverage cansshould be non-toxic and inert, and, if applied to the internal surface,should not adversely affect the taste or appearance, e.g. color, of thefood or beverage in the can or contribute to a contamination of thecontents of the can. Resistance to “popping”, “blushing” and/or“blistering” is also desired. Certain coatings are particularlyapplicable for application onto coiled metal stock, such as the coiledmetal stock from which the ends of cans are made, “can end stock” andvalve cups, e.g. top ends of aerosol cans. Since coatings designed foruse on can end stock are applied prior to the ends being cut and stampedout of the coiled metal stock, they are also typically flexible and/orextensible. For example, can end stock is typically coated on bothsides. Thereafter, the coated metal stock is punched and may be beadedor bent. It may also be scored for the “pop-top” opening and the pop-topring is then attached with a pin that is separately fabricated. The endis then attached to the can body by an edge rolling process.Accordingly, the coating applied to the can end stock typically has acertain degree of toughness and flexibility, such that it can withstandextensive fabrication processes, in addition to some or all of the otherdesirable features discussed above. Various coatings such as epoxy-basedand polyvinyl chloride-based, e.g. organosol type, coatings have beenused in the past to coat the interior of metal cans to preventcorrosion. However, there is a need for food and beverage can liners aswell as non-food container liners that provide improved properties suchas having resistance to degradation in corrosive media as well asappropriate level of flexibility.

SUMMARY OF THE INVENTION

The present disclosure provides for a coating composition that includes40 to 80 weight percent (wt. %) of a base polymer; 5 to 15 wt. % of apolymeric coupling agent; 10 to 30 wt. % of a polymeric stabilizingagent; 0 to 35 wt. % of a polymeric performance improving agent; aneutralizing agent that partially or fully neutralizes the polymericstabilizing agent; and a fluid medium, where the percent values arebased on the total weight of the base polymer, the polymeric couplingagent, the polymeric stabilizing agent and, when present, the polymericperformance improving agent of the coating composition and sum to avalue of 100 wt. %.

For the embodiments of the present disclosure, the base polymer can beselected from the group consisting of a non-functionalized ethylenepolymer, a non-functionalized propylene polymer, a non-functionalizedpropylene/ethylene copolymer, and a combination thereof. For example,the non-functionalized ethylene polymer can be selected from the groupconsisting of polyethylene, a polyethylene-copolymer and a combinationthereof. The non-functionalized ethylene polymer, non-functionalizedpropylene polymer, or non-functionalized ethylene/propylene copolymercan have a crystalline melting point of 100° C. to 230° C. For theembodiments of the present disclosure, the base polymer can also be anon-functionalized propylene polymer.

For the embodiments of the present disclosure, the polymeric stabilizingagent can be an ethylene-acrylic acid and ethylene-methacrylic acidcopolymer having a functionality in a range of 10 wt. % to 25 wt. %. Thepolymeric coupling agent can be selected from the group consisting of afunctionalized polypropylene, a functionalized polyethylene homopolymer,a copolymer that has been modified with carboxylic acid groups, acopolymer that has been modified with anhydride groups and a combinationthereof. The polymeric performance improving agent can be selected fromthe group consisting of functionalized polyethylene, functionalizedpolypropylene, non-functionalized copolymer of ethylene and propyleneand a combination thereof. The neutralizing agent can be a volatilebase. For embodiments of the present disclosure, the volatile base canbe N,N-dimethylethanolamine.

For the embodiments of the present disclosure, the coating compositioncan be used to form a coating layer. In one embodiment, the coatinglayer is on a substrate. The substrate can be selected from the groupconsisting of a metal, a polyurethane, a cured epoxy, a cement or acombination thereof.

Embodiments of the present disclosure also include a method of forming acoating layer that includes applying a coating composition to asubstrate, where the coating composition includes: 40 to 80 weightpercent (wt. %) of a base polymer; 5 to 15 wt. % of a polymeric couplingagent; 10 to 30 wt. % of a polymeric stabilizing agent; 0 to 35 wt. % ofa polymeric performance improving agent; a neutralizing agent thatpartially or fully neutralize the polymeric stabilizing agent; and afluid medium, where the percent values are based on the total weight ofthe base polymer, the polymeric coupling agent, the polymericstabilizing agent and, when present, the polymeric performance improvingagent of the coating composition and sum to a value of 100 wt. %; anddrying the coating composition on the substrate to form the coatinglayer.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention provides an aqueous dispersion, a coatingcomposition, coating layers and coated article made therefrom.

In one embodiment, the instant invention provides an aqueous dispersioncomprising the melt blending product of: (a) from 50 to 99 percent byweight of one or more first polyesters, based on the total solid contentof the dispersion, wherein said one or more first polyesters have anacid number in the range of from less than 15, for example less than 10,or in the alternative less than 5, based on the total solid content ofthe first polyester; (b) from 1 to 50 percent by weight of one or morestabilizing agents comprising at least one second polyester, based onthe total solid content of the dispersion, wherein said second polyesterhas a carboxylic acid group and an acid number greater than 15, forexample greater than 20, based on the solid content of the secondpolyester; (c) one or more neutralizing agents; and (d) from 15 to 90percent by weight of water, based on the total weight of the dispersion;wherein said dispersion has a solid content of 10 to 85 percent, basedon the total weight of the dispersion.

In an alternative embodiment, the instant invention further provides amethod for producing a aqueous dispersion comprising the steps of: (1)selecting one or more first polyesters having an acid number in therange of from less than 15, for example less than 10, or in thealternative less than 5, based on the total solid content of the firstpolyester; (2) selecting one or more stabilizing agents comprising atleast one second polyester having an acid number greater than 15, forexample greater than 20, based on the total solid content of the secondpolyester; (3) selecting one or more neutralizing agents; (4)melt-blending said one or more first polyesters, one or more stabilizingagents in the presence of water and one or more neutralizing agents; (4)thereby producing an aqueous dispersion having a solid content of 10 to85 percent, based on the total weight of the dispersion.

In another alternative embodiment, the instant invention furtherprovides a coating composition comprising: (a) the inventive aqueousdispersion, as described hereinabove; (b) one or more cross-linkingagents; (c) optionally one or more selected from the group consisting ofa polyolefin dispersion, acrylic latex, epoxy resin dispersion,polyurethane dispersion, alkyd dispersion, vinyl acetate dispersion, andethylene vinyl acetate dispersion.

In another alternative embodiment, the instant invention furtherprovides a coating layer comprising at least one or more film layersderived from the inventive coating composition, as describedhereinabove.

In another alternative embodiment, the instant invention furtherprovides a coated article comprising: (1) one or more substrates; (2) atleast one or more coating layers derived from the inventive coatingcomposition, as described hereinabove.

In another alternative embodiment, the instant invention furtherprovides a method for making a coated article comprising the steps of:(1) selecting a substrate; (2) selecting the inventive coatingcomposition, as described hereinabove; (3) applying said coatingcomposition to at least one surface of said substrate; (4) removing atleast a portion of the water from said the coating composition; (5)thereby forming one or more coating layers associated with saidsubstrate; and (6) thereby forming said coated substrate into a coatedarticle.

In another alternative embodiment, the instant invention furtherprovides a method for making a coated article comprising the steps of:(1) selecting a substrate; (2) forming said substrate into article; (3)selecting the coating composition, as described hereinabove; (4)applying said the coating composition to at least one surface of saidarticle; (5) removing at least a portion of the water from said thecoating composition; (6) thereby forming one or more coating layersassociated with at least one surface of said article; and (7) therebyforming said coated article.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the first polyester has a glass transitiontemperature (T_(g)) of at least 30° C.; for example at least 40° C.; orin the alternative, at least 50° C.; or in the alternative, at least 60°C.; or in the alternative, at least 70° C.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the substrate is a pre-coated substrate.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the substrate is metal, wood, paper, plastic,glass, leather, and/or concrete.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the dispersion and/or the coating compositionderived therefrom further comprises a catalyst.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the first polyester is a linear saturatedaromatic polyester with a glass transition temperature of greater than50° C. and an acid number of less than 5 mg KOH/g, and the secondpolyester is compatible with the first polyester, such that a dispersionwith a volume average particle size of less than 5 microns is produced.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the aqueous dispersion and/or the coatingcompositions derived therefrom further comprise one or more bindercompositions such as acrylic latex, vinyl acrylic latex, styrene acryliclatex, vinyl acetate ethylene latex, polyurethane dispersion, alkyddispersion, epoxy dispersion, polyolefin dispersion, and combinationsthereof; optionally one or more fillers; optionally one or moreadditives such as catalysts, wetting agents, defoamers, flow agents,release agents, slip agents, anti-blocking agents, additives to masksulfur staining, pigment wetting/dispersion agents, anti-settlingagents, UV stabilizers, adhesion promoters; optionally one or morelubricants such as fatty acid ester wax, silicon-based wax,fluorine-based wax, polyethylene or any other similar polyolefin wax,carnauba wax, lanolin wax or the like; optionally one or more corrosioninhibitors such as aluminum, and zinc: optionally one or more pigments,e.g. titanium dioxide, barium sulfate, mica, calcium carbonate, silica,zinc oxide, milled glass, aluminum trihydrate, talc, antimony trioxide,fly ash, and clay or the like; optionally one or more co-solvents, e.g.glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate,alcohols, mineral spirits, aromatic solvents and benzoate esters or thelike; optionally one or more dispersants, e.g. aminoalcohols, andpolycarboxylates; optionally one or more surfactants; optionally one ormore preservatives, e.g. biocides, mildewcides, fungicides, algaecides,and combinations thereof; optionally one or more thickeners, e.g.cellulosic based thickeners such as hydroxyethyl cellulose,hydrophobically modified alkali soluble emulsions (HASE thickeners suchas UCAR POLYPHOBE TR-116) and hydrophobically modified ethoxylatedurethane thickeners (HEUR); or optionally one or more additionalneutralizing agents, e.g. hydroxides, amines, ammonia, and carbonates;optionally one or more solvents or coalescing agents.

Aqueous Dispersion

The aqueous dispersion according to the present invention comprises themelt blending product of: (a) from 50 to 99 percent by weight of one ormore first polyesters, based on the total solid content of thedispersion, wherein said one or more first polyesters have an acidnumber in the range of from less than 15, for example less than 10, orin the alternative less than 5, based on the total solid content of thefirst polyester; (b) from 1 to 50 percent by weight of one or morestabilizing agents comprising at least one second polyester, based onthe total solid content of the dispersion, wherein said second polyesterhas a carboxylic acid group and an acid number equal to or greater than15, for example greater than 20, based on the solid content of thesecond polyester; (c) one or more neutralizing agents; and (d) from 15to 90 percent by weight of water, based on the total weight of thedispersion; wherein said dispersion has a solid content of 10 to 85percent, based on the total weight of the dispersion.

First Polyester

The aqueous dispersion comprises from 50 to 99 percent by weight of oneor more first polyesters based on the total weight of the solid contentof the aqueous dispersion. All individual values and subranges from 50to 99 weight percent are included herein and disclosed herein; forexample, the weight percent can be from a lower limit of 50, 55, 60, 65,or 70 weight percent to an upper limit of 60, 65, 70, 75, 80, 85, 90,95, or 99 weight percent. For example, the aqueous dispersion maycomprise from 55 to 95 percent by weight of one or more first polyester,based on the total weight of the solid content of the aqueousdispersion; or in the alternative, the aqueous dispersion may comprisefrom 60 to 90 percent by weight of one or more first polyester, based onthe total weight of the solid content of the aqueous dispersion; or inthe alternative, the aqueous dispersion may comprise from 65 to 90percent by weight of one or more first polyester, based on the totalweight of the solid content of the aqueous dispersion; or in thealternative, the aqueous dispersion may comprise from 75 to 95 percentby weight of one or more first polyester, based on the total weight ofthe solid content of the aqueous dispersion. The aqueous dispersioncomprises at least one or more first polyesters. The first polyester isa thermosetting polyester. Suitable thermosetting polyesters(hydrophobic polyester) for use in the present invention include, butare not limited to, hydroxyl functional polyesters with medium to highmolecular weight (>5000 g/mol Mw, preferably >10,000 g/mol M_(w), andmost preferably >20,000 g/mol M_(w)) polyester. Typically the hydroxylnumber of the thermosetting polyester will be at least 3 mg KOH/g (basedon resin solids) and preferably at least 5 mg KOH/g. The thermosettingpolyester will typically have an acid number of <15 mg KOH/g (based onresin solids), preferably <10 mg KOH/g, and most preferably <5 mg KOH/g.Preferred polyester thermosetting resins have a glass transitiontemperature (T_(g)) of at least about 30° C., preferably greater than50° C., and most preferably greater than 70° C.

The hydroxyl functional thermosetting polyester may be formed byconventional polycondensation techniques such as for example describedin Zeno W. Wicks, Jr, Frank N. Jones, S. Peter. Pappas, “OrganicCoatings, Science and Technology,” pp 246-257 (John Wiley & Sons, 1999,second edition) and references therein or in Houben-Weyl, “Methoden derOrganischen Chemie, Band E20, Makromolekulare Soffe, Polyester,” pp1405-1429. (Georg Thieme Verlag, Stuttgart 1987) and references therein.In one embodiment, a diol or polyol and a di-carboxylic acid orpolycarboxylic acid are charged into a conventional polymerizationvessel and reacted between about 150° C. and 280° C. for several hours.Optionally, an esterification catalyst may be used to decrease thereaction time. In general, to ensure the formation of a hydroxyl-groupterminated polyester, a small excess of diol may be used. It is alsounderstood that an esterifiable derivative of a polycarboxylic acid,such as a dimethyl ester or anhydride of a polycarboxylic acid, can beused to prepare the polyester.

In one embodiment of the invention, the thermosetting polyester is alinear saturated polyester. However, in some cases it might be desirableto introduce some branching points into the polyester. Triols or polyolsor polyacids can be used to provide branched polyesters.

Suitable and typical dicarboxylic acids or polycarboxylic acids, ortheir corresponding alkyl esters, that may be used to form thethermosetting polyester include saturated as well as unsaturateddicarboxylic acids such as, but not limited to, for example, isophthalicacid, maleic acid, maleic anhydride, malonic acid, fumaric acid,succinic acid, succinic anhydride, glutaric acid, adipic acid,2-methyl-1,6-hexanoic acid, pimelic acid, suberic acid, dodecanedioicacids, phthalic acid, phthalic anhydride, 5-tert butyl isophthalic acid,tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalicanhydride, endomethylenetetrahydrophthalic anhydride, azelaic acid,sebacic acid, tetrachlorophthalic anhydride, chlorendic acid,isophthalic acid, trimellitic anhydride, terephthalic acid, naphthalenedicarboxylic acid, cyclohexane-dicarboxylic acid, dimer fatty acid, oranhydrides of any of these acids, or mixtures thereof.

Suitable diols and polyols that may be used to form the thermosettingpolyester include, but are not limited to, for example, ethylene glycol,diethylene glycol, triethylene glycol and higher polyethylene glycols,propylene glycol, dipropylene glycol, tripropylene glycol and higherpolypropylene glycols, 1,3-propanediol, 1,4-butanediol and otherbutanediols, 1,5-pentanediol and other pentane diols, hexanediols,decanediols, and dodecanediols, glycerol, trimethylolpropane,trimethylolethane, neopentyl glycol, pentaerythritol,cyclohexanedimethanol, dipentaerythtritol, 1,2-methyl-1,3-propanediol,1,4-benzyldimethanol, 2,4-dimethyl-2-ethylhexane-1,3-diol,isopropylidene bis (p-phenylene-oxypropanol-2),4,4′-dihydroxy-2,2′-diphenylpropane, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol (or mixtures of 1,3 and 1,4cyclohexanedimethanol, may be cis or trans), sorbitol, or mixturesthereof.

Suitable thermosetting polyesters are available, for example, fromEVONIK under the tradename DYNAPOL®.

In one embodiment, the hydroxyl functional, first polyester, may firstbe reacted with one or more multi-functional isocyanates such as, forexample, isophorone diisocyanate (IPDI), hexamethylene diisocyanate(HDI), dicyclohexylmethane-4,4′-diisocyanate (H12MDI), and 1,3 or1,4-bis(isocynatomethyl)cyclohexane, or mixtures thereof, to produce ahydroxyl-functional polyester-carbamate polymer.

In another embodiment, the hydroxyl functional, thermosetting polyestermay first be reacted with one or more partially blocked isocyanates orpolyisocyanates. In a preferred embodiment, the partially blockedisocyanate is a polyisocyanurate compound, such as a trimer, having atleast one free isocyanate group. More preferably, the blocked isocyanatehas at least two unblocked isocyanate groups. The blocked isocyanategroups of the at least partially blocked polyisocyanate can be anycombination of deblockable and/or non-deblockable isocyanate groups.Preferred blocking agents for forming deblockable isocyanate groupsinclude, but are not limited to ε-caprolactam, diisopropylamine (DIPA),methyl ethyl ketoxime (MEKO), and/or mixtures thereof. Preferredblocking agents for forming non-deblockable isocyanate groups include,but are not limited to, glycidol, hydroxyethyl acrylate, alcohols, andglycols. In one preferred embodiment, the deblockable isocyanate groupsdo not appreciably deblock at a temperature of less than 50° C., morepreferably the isocycanate groups do not appreciably deblock at atemperature of less than 100° C.

Stabilizing Agent Comprising a Second Polyester

The aqueous dispersion further comprises at least one or morestabilizing agents comprising one or more second polyesters to promotethe formation of a stable dispersion. The second polyester has acarboxylic acid group and an acid number equal to or greater than 15,for example greater than 20. The aqueous dispersion comprises 1 to 50percent by weight of one or more stabilizing agents, based on the totalweight of the solid content of the dispersion. All individual values andsubranges from 1 to 50 weight percent are included herein and disclosedherein; for example, the weight percent can be from a lower limit of 1,3, 5, 10 weight percent to an upper limit of 15, 25, 35, 45, or 50weight percent. For example, the dispersion may comprise from 1 to 25;or in the alternative, from 1 to 35; or in the alternative, from 1 to40; or in the alternative, from 1 to 45 percent by weight of one or morestabilizing agents, based on the total weight of the solid content ofthe dispersion.

The second polyester is a high acid, water dispersible, hydrophilicpolyester, which is used as the primary stabilizing agent for dispersingthe first polyester resin. The second polyester typically has an acidnumber in the range of from equal to or greater than 15 mg KOH/g (basedon resin solids), for example from 20 to 80 mg KOH/g (based on resinsolids). The carboxylic acid functionality of the second polyester iscritical to the present invention. In producing the waterbornedispersion, the acid functionality of the second polyester isneutralized with a suitable inorganic or organic base to providecolloidal stability. The high acid stabilizing polyester may also havehydroxyl functionality, but this is not required. Preferably the highacid stabilizing polyester has an OH number of at least 2 mg KOH/g(based on resin solids), preferably 5 mg KOH/g or greater, and mostpreferably 20 mg KOH/g or greater. The high acid stabilizing polyestermay be produced by conventional polycondensation techniques such as forexample described in Zeno W. Wicks, Jr, Frank N. Jones, S. Peter. Pappas“Organic Coatings, Science and Technology,” pp 246-257 (John Wiley &Sons, 1999, second edition) and references therein or in Houben-Weyl,“Methoden der Organischen Chemie, Band E20, Makromolekulare Soffe,Polyester” pp 1405-1429. (Georg Thieme Verlag, Stuttgart 1987) andreferences therein. In one embodiment, a diol or polyol and adi-carboxylic acid or polycarboxylic acid are charged into aconventional polymerization vessel and reacted between about 150° C. and280° C. for several hours. Optionally, an esterification catalyst may beused to decrease the reaction time. It may be preferable to use atwo-step process to provide a carboxyl functional polyester. In oneembodiment, an OH-functional polyester is first prepared so that thereis little, if any, free carboxylic acid and/or carboxylate functions,and which then in a subsequent step is reacted with a cyclicdicarboxylic anhydride, in a ring-opening and monoester-formingreaction, with free carboxylic acid and/or carboxylate groups then beingformed. The excess of OH functionality in the resin of the first step isdesigned in such a way that the final resin, after the reaction with thepolyacid functional molecules, will provide a carboxyl terminatedpolyester resin in which the acid number is typically in the range offrom equal to or greater than 15 mg KOH/g (based on resin solids), forexample from 20 to 80 mg KOH/g (based on resin solids).

The carboxylic acid component of the high acid stabilizing polyester maycontain one or more aliphatic, cycloaliphatic, araliphatic, and/oraromatic carboxylic acids with a COOH functionality of at least two, oranhydrides thereof. Suitable and typical dicarboxylic acids orpolycarboxylic acids, or their corresponding alkyl esters, that may beused to form the high acid stabilizing polyester include, but are notlimited to, saturated as well as unsaturated dicarboxylic acids such as,for example, but not limited to, maleic acid, maleic anhydride, malonicacid, fumaric acid, succinic acid, succinic anhydride, glutaric acid,adipic acid, 2-methyl-1,6-hexanoic acid, pimelic acid, suberic acid,dodecanedioic acids. phthalic acid, phthalic anhydride, 5-tert butylisophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid,hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride,azelaic acid, fumaric acid, sebacic acid, tetrachlorophthalic anhydride,chlorendic acid, isophthalic acid, trimellitic anhydride, terephthalicacid, naphthalene dicarboxylic acid, cyclohexane-dicarboxylic acid, andmixtures thereof.

The glycol component of the high acid stabilizing polyester may beethylene glycol, diethylene glycol, triethylene glycol and/or higherpolyethylene glycols, propylene glycol, dipropylene glycol, tripropyleneglycol and/or higher polypropylene glycols, 1,3-propanediol,1,4-butanediol and other butanediols, 1,5-pentanediol and/or otherpentane diols, hexanediols, decanediols, and/or dodecanediols, glycerol,trimethylolpropane, trimethylolethane, neopentyl glycol,pentaerythritol, cyclohexanedimethanol, a polyethylene or polypropyleneglycol having a molecular weight of about 500 or less,dipentaerythtritol, 1,3-butyleehtylpropanediol,2-methyl-1,3-propanediol, 1,4-benzyldimethanol,2,4-dimethyl-2-ethylhexane-1,3-diol, isopropylidene his(p-phenylene-oxypropanol-2), and mixtures thereof. In some embodiments,the aliphatic glycol may contain from 2 to 8 carbon atoms1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol (or mixtures of 1,3and 1,4 cyclohexanedimethanol, may be cis or trans),2,2,4,4-tetramethyl-1,3-cyclobutanediol (may be cis, trans, or a mixturethereof) 4,4′-dihydroxy-2,2′-diphenylpropane or mixtures thereof.

The composition of the high acid stabilizing polyester (secondpolyester) must be chosen so that it exhibits good compatibility withthe first polyester. If the compatibility is poor, a good water bornedispersion with small particle size (typically less than about 5 micronvolume average particle size diameter) and good stability may not beproduced. In addition, resulting coatings from such dispersions may havepoor appearance and may show reduced performance in coatings evaluationtests because of lack of compatibility. For example, if an aliphatic,high acid polyester (second polyester) is used to disperse an aromatic,hydrophobic first polyester, a poor dispersion will typically resultwith large particle size (typically greater than 5 micron volume averageparticle size diameter). One way to assess compatibility is to melt mixthe first polyester and the second polyester at a temperature abovetheir respective melting points. A blend with good compatibility willtypically result in a relatively clear or translucent blend, while anincompatible blend will typically result in an opaque or hazy, whitemelt blend. There may be other methods to determine compatibility suchas morphology determination by optical microscopy or transmissionelectron microscopy of the blend.

In selected embodiments, the stabilizing agent may optionally include asurfactant. Other stabilizing agents that may be used include, but arenot limited to, long chain fatty acids, fatty acid salts, or fatty acidalkyl esters having from 12 to 60 carbon atoms. In other embodiments,the long chain fatty acid or fatty acid salt may have from 12 to 40carbon atoms.

Additional stabilizing agents that may be useful in the practice of thepresent invention include, but are not limited to, cationic surfactants,anionic surfactants, or non-ionic surfactants. Examples of anionicsurfactants include, but are not limited to, sulfonates, carboxylates,and phosphates. Examples of cationic surfactants include, but are notlimited to, quaternary amines. Examples of non-ionic surfactantsinclude, but are not limited to, block copolymers containing ethyleneoxide and silicone surfactants. Stabilizing agents useful in thepractice of the present invention can be either external surfactants orinternal surfactants. External surfactants are surfactants that do notbecome chemically reacted into the base polymer during dispersionpreparation. Examples of external surfactants useful herein include, butare not limited to, salts of dodecyl benzene sulfonic acid and laurylsulfonic acid salt. Internal surfactants are surfactants that do becomechemically reacted into the base polymer during dispersion preparation.An example of an internal surfactant useful herein includes2,2-dimethylol propionic acid and its salts. Additional surfactants thatmay be useful in the practice of the present invention include cationicsurfactants, anionic surfactants, non-ionic surfactants, or combinationsthereof. Various commercially available surfactants may be used inembodiments disclosed herein, including: OP-100 (a sodium stearate),OPK-1000 (a potassium stearate), and OPK-181 (a potassium oleate), eachavailable from RTD Hallstar; UNICID 350, available from Baker Petrolite;DISPONIL FES 77-IS, DISPONIL TA-430, Disponil FES-32, and DiponilFES-993, each available from Cognis; RHODAPEX CO-436, SOPROPHOR 4D384,3D-33, and 796/P, RHODACAL BX-78 and LDS-22, RHODAFAC RE-610, andRM-710, and SUPRAGIL MNS/90, each available from Rhodia; and TRITONQS-15, TRITON W-30, DOWFAX 2A1, DOWFAX 3B2, DOWFAX 8390, DOWFAX C6L,TRITON X-200, TRITON XN-45S, TRITON H-55, TRITON GR-5M, TRITON BG-10,and TRITON CG-110, each available from The Dow Chemical Company,Midland, Mich., and ESPERSE grades E-100, E-506, E-328, E-355, andE-600, each available from Ethox Chemicals, LLC.

Additional stabilizing agents which could be used are solution orsuspension polymers consisting of ethylenically unsaturated monomerssuch as acrylic and/or methacrylic acid and their (C₁-C₃₀) esters oramides; acrylamide/methacrylamide and their N-substituted derivatives;acrylonitrile; styrene and substituted styrene derivatives.

Exemplary polymeric stabilizing agents include, but are not limited to,amphiphilic copolymer compositions, the copolymer comprising thereaction product of (i) from 5 to 95 wt. % of one or more hydrophilicmonomers and (ii) from 5 to 95 wt. % of one or more copolymerizableethylenically unsaturated hydrophobic monomers. These materials arewater soluble or emulsifiable, especially upon neutralization and canact as colloidal stabilizers. Exemplary stabilizing agents, for example,include, but are not limited to, butylacrylate and laurylmethacrylate.

Representative nonionic, water-soluble monomers suitable for productionof amphiphilic copolymer compositions, include, but are not limited to,acrylamide, methacrylamide, N,N-dimethylacrylamide,N,N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide,N-vinylmethylacetamide, N-vinyl pyrrolidone, hydroxyethyl methacrylate,hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropylmethacrylate, t-butylacrylamide, N methylolacrylamide,alkyl(meth)acrylates such as methyl(meth)acrylate, butyl acrylate andethylacrylate, vinyl monomers such as ethylene, styrene, divinylbenzene,di-isobutylethylene, vinyl acetate and N-vinyl pyrrolidone, and allylmonomers such as allyl (meth)acrylate.

Representative cationic, water-soluble monomers suitable for productionof amphiphilic copolymer compositions include, but are not limited to,quaternary ammonium salts of amine functionalized monomers such asacrylamide, methacrylamide, N,N-dimethylacrylamide,N,N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide,N-vinylmethylacetamide, N-vinyl pyrrolidone, t-butylacrylamide,N-methylolacrylamide, tributylammonium ethyl(meth)acrylate TBAEMA,DMAEMA, DMAPMAM, diallyldimethylammonium chloride (DADMAC),methylacrylamidopropyltrimethylammonium chloride (MAPTAC),acrylamidopropyltrimethylammonium chloride (APTAC), N-vinyl pyrrolidone,vinylimidazole, polyquaternium-11 and polyquaternium-4.

“Anionic” or “acid-containing monomer” suitable for production ofamphiphilic copolymer compositions include, but are not limited to,ethylenically unsaturated monomers containing carboxylic acid,phosphonic acid, phosphinic acid, sulfinic acid and sulfonic acidgroups. Suitable examples include (meth)acrylic acid, maleic acid,succinic acid, itaconic acid, vinyl phosphonic acid and vinylsulfonicacid.

In an alternative embodiment, one or more stabilizing agents may bebased on resins such as polyester, epoxy resins, polyamide resins, whichmight be reacted with acrylic resins or acrylic monomers to formpolyester acrylate, polyamide acrylates epoxy resin acrylates.

Polyester acrylates as stabilizing agents may be formed via in-situpolymerization of copolymerizable ethylenically unsaturated monomers inpresence of polyesters. Examples include ethylenically unsaturated mono-or polyfunctional acids, ethylenically unsaturated mono- orpolyfunctional acid esters, amides, nitriles as well as vinyl monomersand vinyl ester with a polyester in or without presence of a reactionfluid. Polyester acrylates in solvents can be dried according tosuitable methods known to those of ordinary skill in the art.

Suitable epoxy resins for producing stabilizing agents may be obtainedin accordance with conventional procedures well known to those ofordinary skill in the art by reacting a polyepoxide with a suitablepolynucleophile. Suitable epoxides include, but are not limited to,glycidyl ethers, and other epoxy group containing molecules. Suitablepolynucleophiles include, but are not limited to, polyhydric phenols,and poly phenols, polythiols, aliphatic polyalcohols or polybasic acidsor polyamines. Exemplary suitable epoxies, for example, include, but arenot limited to, glycidyl ether that contains at least two glycidyl ethergroups per polyglycidyl ether molecule (e.g. an at least diglycidylether) with a polyhydric phenol that contains at least two hydroxylgroups in the polyhydric polyphenol (e.g., at least dihydric phenol or adiphenol) in presence of a conventional catalyst at an elevatedtemperature with or without solvent present. Another class of epoxyresins may be obtained in accordance with conventional procedures wellknown to those of ordinary skill in the art by reacting, for example, apolyglycidyl ether that contains at least two glycidyl ether groups perpolyglycidyl ether molecule (e.g. an at least diglycidyl ether) with apolybasic acid that contains at least two carboxyl groups per polybasicacid molecule (e.g. an at least dibasic polycarboxylic acid) in presenceof a conventional catalyst at an elevated temperature with or withoutsolvent present.

Epoxy acrylates for producing stabilizing agents may be formed viain-situ polymerization of copolymerizable ethylenically unsaturatedmonomers in presence of epoxy resins. Examples include, but are notlimited to, ethylenically unsaturated mono- or polyfunctional acids,ethylenically unsaturated mono- or polyfunctional acid esters, amides,nitriles as well as vinyl monomers and vinyl ester with an epoxy resinsin or without presence of a reaction fluid. Alternatively a polymericacid functional acrylic resin can be reacted with an epoxy resin in thepresence of a suitable catalyst to form epoxy acrylate. Epoxy acrylatesin solvents can be dried according to suitable methods known to those ofordinary skill in the art. In one embodiment an acid functionalizedpolyester may be used, wherein the epoxy is reacted, for example, withan excess of an acid functional polyester.

Neutralizing Agent

The stabilizing agent may be partially or fully neutralized with aneutralizing agent. In certain embodiments, neutralization of thestabilizing agent, the second polyester, may be from 50 to 250 percenton a molar basis; or in the alternative, it may be from 50 to 200percent on a molar basis; or in the alternative, it may be from 50 to150 percent on a molar basis; or in the alternative, it may be from 50to 120 percent on a molar basis. For example, the neutralizing agent maybe a base, such as ammonium hydroxide, sodium hydroxide, or potassiumhydroxide. Other neutralizing agents can include lithium hydroxide, forexample. In another alternative, the neutralizing agent may, forexample, be a carbonate. In another alternative, the neutralizing agentmay, for example, be any amine such as monoethanolamine, or2-amino-2-methyl-1-propanol (AMP). Amines useful in embodimentsdisclosed herein may include diethanolamine, triethanolamine, and TRISAMINO™ (each available from Angus), NEUTROL™ TE (available from BASF),as well as triisopropanolamine, diisopropanolamine, andN,N-dimethylethanolamine (each available from The Dow Chemical Company,Midland, Mich.). Other useful amines may include ammonia,monomethylamine, dimethylamine, trimethylamine, monoethylamine,diethylamine, triethylamine, mono-n-propylamine, butylamine,dibutylamine, tributylamine, dimethyl benzyl amine, dimethyln-propylamine, N-methanol amine, N-aminoethylethanolamine,N-methyldiethanolamine, monoisopropanolamine, N,N-dimethylpropanolamine, 2-amino-2-methyl-1-propanol, 1,2-diaminopropane,tris(hydroxymethyl)-aminomethane, ethylenediamineN,N,N′N′-tetrakis(2-hydroxylpropyl) ethylenediamine, N,N,N′,N′tetramethylpropanediamine, 3-methoxypropyl amine, imino bis-propyl amineand the like. In some embodiments, mixtures of amines or mixtures ofamines and other surfactants may be used. In one embodiment, theneutralizing agent may be a polymeric amine, e.g. diethylene triamine.Those having ordinary skill in the art will appreciate that theselection of an appropriate neutralizing agent depends on the specificcomposition formulated, and that such a choice is within the knowledgeof those of ordinary skill in the art. In one embodiment, amines withboiling points below 250° C. may be used as the neutralizing agents.

Fluid Medium

The aqueous dispersion further comprises a fluid medium. The fluidmedium may be any medium; for example, the fluid medium may be water.The aqueous dispersion comprises from 15 to 90 percent by weight ofwater, based on the weight of the dispersion; for example, thedispersion comprises from 20 to 85 percent by weight of water, based onthe weight of the dispersion; or in the alternative from 30 to 75percent by weight of water, based on the weight of the dispersion; or inthe alternative from 40 to 75 percent by weight of water, based on theweight of the dispersion; or in the alternative from 40 to 65 percent byweight of water, based on the weight of the dispersion. Water content ofthe dispersion may preferably be controlled so that the solids content(one or more first polyesters plus stabilizing agent comprising a secondpolyester) is in the range of from 10 to 85 percent by weight, based onthe weight of the dispersion. For example, the dispersion comprises from20 to 70 percent by weight of solid contents (one or more firstpolyesters plus stabilizing agent comprising a second polyester), basedon the weight of the dispersion; or in the alternative, from 25 to 70percent by weight of solid contents (one or more first polyesters plusstabilizing agent comprising a second polyester), based on the weight ofthe dispersion; or in the alternative, from 35 to 70 percent by weightof solid contents (one or more first polyesters plus stabilizing agentcomprising a second polyester), based on the weight of the dispersion;or in the alternative, from 35 to 65 percent by weight of solid contents(one or more first polyesters plus stabilizing agent comprising a secondpolyester), based on the weight of the dispersion; or in thealternative, from 40 to 70 percent by weight of solid contents (one ormore first polyesters plus stabilizing agent comprising a secondpolyester), based on the weight of the dispersion; or in thealternative, from 40 to 65 percent by weight of solid contents (one ormore first polyesters plus stabilizing agent comprising a secondpolyester), based on the weight of the dispersion; or in thealternative, from 45 to 65 percent by weight of solid contents (one ormore first polyesters plus stabilizing agent comprising a secondpolyester), based on the weight of the dispersion; or in thealternative, from 50 to 70 percent by weight of solid contents (one ormore first polyesters plus stabilizing agent comprising a secondpolyester), based on the weight of the dispersion.

The fluid medium may optionally contain one or more suitable solvents.For example the one or more optional solvents include but are notlimited to, e.g. glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediolmonoisobutyrate, alcohols, ketones, glycol ether esters, mineralspirits, aromatic solvents and/or esters or the like; optionally one ormore dispersants, e.g. aminoalcohols, and/or polycarboxylates.

Additional Components

The aqueous dispersion of the present invention may optionally beblended with one or more binder compositions such as acrylic latex,vinyl acrylic latex, styrene acrylic latex, vinyl acetate ethylenelatex, epoxy dispersion, polyurethane dispersion, alkyd dispersion,polyolefin dispersion, and combinations thereof; optionally one or morefillers; optionally one or more additives such as catalysts, wettingagents, defoamers, flow agents, release agents, slip agents,anti-blocking agents, additives to mask sulfur staining, pigmentwetting/dispersion agents, anti-settling agents, UV stabilizers,adhesion promoters; optionally one or more lubricants such as fatty acidester wax, silicon-based wax, fluorine-based wax, polyethylene or anyother similar polyolefin wax, carnauba wax, lanolin wax or the like;optionally one or more corrosion inhibitors such as aluminum, and zinc:optionally one or more pigments, e.g. titanium dioxide, barium sulfate,mica, calcium carbonate, silica, zinc oxide, milled glass, aluminumtrihydrate, talc, antimony trioxide, fly ash, and clay or the like;optionally one or more co-solvents, e.g. glycols, glycol ether,2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, alcohols, mineralspirits, aromatic solvents and benzoate esters or the like; optionallyone or more dispersants, e.g. aminoalcohols, and polycarboxylates;optionally one or more surfactants; optionally one or morepreservatives, e.g. biocides, mildewcides, fungicides, algaecides, andcombinations thereof; optionally one or more thickeners, e.g. cellulosicbased thickeners such as hydroxyethyl cellulose, hydrophobicallymodified alkali soluble emulsions (HASE thickeners such as UCARPOLYPHOBE TR-116) and hydrophobically modified ethoxylated urethanethickeners (HEUR); or optionally one or more additional neutralizingagents, e.g. hydroxides, amines, ammonia, and carbonates; optionally oneor more solvents or coalescing agents.

In addition, the aqueous dispersion may be blended with one or moredispersions, emulsions, suspensions, colloidal suspensions, and thelike. For example the aqueous dispersion of the invention may be blendedwith polyurethane dispersion, alkyd dispersion, epoxy dispersion, vinylacetate emulsion, acrylic emulsion, polyolefin dispersion, vinyl acetateethylene emulsion, and/or the like. The addition of the additionalcomponents, as described herein, may be achieved as part of the processfor making the dispersion, i.e. the additional components are addedwhile producing the aqueous dispersion; or in he alternative, theadditional components may added post aqueous dispersion production, i.e.the additional components are added into the aqueous dispersion afterthe dispersion is produced; or in the alternative, combinations thereof,i.e. additional components may be added during the process for makingthe dispersion and additionally such additional components are addedpost dispersion production as well.

Crosslinking Agent

The aqueous dispersion may optionally further comprise at least one ormore crosslinking agents to promote crosslinking and or one or morecatalyst to increase the rate of crosslinking. Such catalysts aregenerally known, and the selection of suitable catalyst typicallydepends on the selection of the crosslinking agent and other factorssuch as conditions for such crosslinking. Such catalysts include, butare not limited to, depending on type of crosslinker—strong acids, weakacids or compounds containing metals, such as dodecyl benzene sulfonicacid, p-toluene sulfonic acid, di-nonylnaphtalene disulfonic acid,methane sulfonic acid, phosphoric acid or weak acids such as ammonium orphosphonium salts or tin, bismuth, zirconium or aluminum chelatecompounds. Exemplary catalysts include, but are not limited to, NACURE™,K-Kure™ and K-Kat™, available from King Industries, CYCAT™ from CytecIndustries, and/or FASCAT™ from Arkema Inc. The aqueous dispersion ofthe instant invention comprises 0.5 to 50 percent by weight of one ormore crosslinking agents, based on the total weight of the solid contentof the dispersion. All individual values and subranges from 0.5 to 50weight percent are included herein and disclosed herein; for example,the weight percent can be from a lower limit of 0.5, 1, 3, 5, 10. 15, or20 weight percent to an upper limit of 10, 12, 15, 18, 20, 25, 30, 35,40, 45, or 50 weight percent. For example, the dispersion may comprisefrom 1 to 18; or in the alternative, from 1 to 15; or in thealternative, from 1 to 12; or in the alternative, from 1 to 10; or inthe alternative, from 1 to 20; or in the alternative, from 1 to 30; orin the alternative, from 1 to 40; or in the alternative, from 1 to 45;or in the alternative, from 1 to 50 percent by weight of one or morecrosslinking agents, based on the total weight of the solid content ofthe dispersion. In selected embodiments the crosslinking agent may, forexample, be phenol-formaldehyde resins, amino-formaldehyde resinsincluding, but not limited, to urea-formaldehyde resins, melamineformaldehyde resins, benzoguanamine formaldehyde resins, anhydrideresins, epoxy group containing resins such as epoxy resins, epoxy groupcontaining polyester or acrylic resins and blocked or un-blockedisocyanate resins, and combinations of two or more thereof, providedthat the combinations of such crosslinkers is compatible.

Crosslinking agent may be a compound, which reacts with a reactivefunctional group contained in the dispersion formulation; therebyfacilitating their crosslinking. Such functional groups can be presentin both the first polyester as well as the stabilizing agent comprisinga second polyester.

For example, reactive functional groups include, but are not limited to,acid groups such as carboxylic acid groups, free or in the neutralizedform, or any functional groups having another active hydrogen by anothercomponent such as alcohol groups, amino groups, epoxy groups, or thelike.

Crosslinkable functional groups in the cross-linking agent are groupscapable of reacting with the reactive functional group of the firstpolyester or the stabilizing agent comprising a second polyester. Forexample, a carbodiimide group, an oxazoline group, an isocyanate group,an epoxy group, a methylol group, an aldehyde group, an acid anhydridegroup, a hydroxy group, an aziridinyl group or a silane group can beused in a crosslinker.

Another possibility of crosslinking acid functional groups is by use ofmultivalent metal ions by reaction of the aforementioned acid groupswith a multivalent metal ion containing substance, such as zinc oxide.

Carboxylic acids could also be crosslinked in reactions withmultifunctional olefinic unsaturated substances under catalysis of astrong acid. Multifunctional carbonates could also react with carboxylicacids to give ester linkages with liberation of carbon dioxide.

In the alternative, crosslinking may be accomplished via free radicalcrosslinking, initiated by addition of peroxides or via radiation, e.g.,electron beam.

With respect to crosslinkable functional groups, one or more may bepresent in a crosslinking agent. In the alternative, two or morecrosslinkable functional groups may be present in a single molecule.

The cross-linking agent having the above described crosslinkablefunctional group may be a waterdispersed or waterdispersible orwater-soluble substance. In one embodiment, exemplary crosslinkingagents include, but are not limited to, an aqueous monomeric orpolymeric substance, which contains two or more oxazoline groups,carbodiimide groups, epoxy groups, isocyanate groups, methylol groupsetc. or several of these per molecule.

An exemplary oxazoline crosslinking agent is an aqueous polymer havingtwo or more oxazoline groups in its molecules, substances can beobtained by polymerizing an oxazoline group-containing monomer and, asrequired, an ethylenic unsaturated monomer. Alternatively an oxazolinecrosslinking agent can also be obtained by reaction between a nitrilegroup and an aminoethanol group, dehydration of a hydroxylalkylamidegroup and the like.

Crosslinking agents having two or more carbodiimide groups can beproduced from diisocyanate compounds by a condensation reactionaccompanied by decarboxylation reaction of a diisocyanate compound.Examples of the diisocyanate compound include, but are not limited to,1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate,4,4′-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate,2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexanemethylenediisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate,isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate,methylcyclohexane diisocyanate, and tetramethylxylylene diisocyanate andthe like. These compounds may also be used as mixtures.

Monofunctional isocyanates may be included to control the resinmolecular chain length such as phenyl isocyanate, tolyl isocyanate,cyclohexylisocyanate, dimethylphenyl isocyanate, butylisocyanate, andnaphthyl isocyanate are useful.

Diisocyanate substances may be partially reacted with aliphaticcompounds, alicyclic compounds, or aromatic compounds having a hydroxylgroup, an imino group, an amino group, a carboxyl group, a mercaptogroup, an epoxy group, and the like.

In the condensation reaction accompanied by decarboxylation of adiisocyanate compound, a carbodiimidization catalyst can be used. Usableas such a catalyst are, for example, phospholene oxides such as1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide,1-ethyl-2-phospholene-1-oxide, and 3-phospholene isomers thereof.

In order to convert a carbodiimide group-containing polymer into anaqueous polymer, a hydrophilic segment is provided in the molecularstructure of the carbodiimide group-containing polymer. For example, anaqueous polymer containing a carbodiimide group can be obtained byproviding a hydrophilic segment having a functional group which hasreactivity with an isocyanate group. Usable as the hydrophilic segmentare: quaternary ammonium salts of dialkylamino alkylamine (e.g.,quaternary ammonium salts of 2-dimethylaminoethanol); quaternary saltsof dialkylamino alkylamine (e.g., 3-dimethylamino-n-propylamine); alkylsulfonic acid salts having at least one reactive hydroxyl group (e.g.,sodiumhydroxypropanesulfonate); a mixture of polyethylene oxide orpolyethylene oxide, whose terminal is capped with an alkoxy group, and apolypropylene oxide (e.g., polyethylene oxide whose terminal position iscapped with a methoxy group or an ethoxy group).

As an aqueous cross-linking agent containing an epoxy group, there areexemplified sorbitol polyglycidyl ether, glycerol triglycidyl ether,polyglycerol polyglycidylether trimethylolpropane triglycidyl ether,poly(ethyleneglycol) diglycidyl ether, poly(propyleneglycol) diglycidylether, phenol ethyleneoxide glycidyl ether, and lauryl alcoholethyleneoxide glycidyl ether or the like. In addition to the above,mentioned as examples are: a water-soluble epoxy resin obtained byreacting a carboxy compound, which is obtained through a reactionbetween a polyoxyethylene polyol compound and an acid anhydridecompound, and an epoxy resin having two or more epoxy groups in itsmolecules; and a self-emulsifiable epoxy resin composition obtained bymixing the water-soluble epoxy resin and the epoxy resin having two ormore epoxy groups in its molecules. Such resins can be obtained forexample under the tradenames of XZ 92533.00, XZ 92598.00 and XZ 92446.00from The Dow Chemical Company, Midland, Mich. Examples of the anhydridecompound include, but not particularly limited to, preferably aromaticanhydrides such as phthalic anhydride, trimellitic anhydride, andpyromellitic anhydride; and cyclic aliphatic anhydrides such as maleicanhydride, succinic anhdyride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, alkenyl succinicanhdyride, hexahydrophthalic anhydride, and methyl hexahydrophthalicanhydride. There is no limitation on the epoxy resin having two or moreepoxy groups in its molecules, and all known epoxy resins with an epoxyfunctionality of greater or equal to two can be used. Examples arepolyglycidyl ether obtained from epichlorohydrin and a polyhydriccompound such as, phenol novolac, and cresol novolac bisphenol A,bisphenol F, bisphenol S, resorcinol, hydroquinone or catechol; alkyleneoxide-added bisphenol A; polyalcohols such as polypropylene glycol,1,6-hexanediol, trimethylol propane, glycerin, cyclohexanedimethanol;and polyglycidyl ester and polyglycidyl amine of polycarboxylic acidssuch as adipic acid, phthalic acid, dimer acid and the like.

Aqueous cross-linking agent containing an isocyanate group are, forexample: polyisocyanate mainly containing at least one member selectedfrom the group consisting of an isocyanurate group-containingpolyisocyanate, an urethodione group-containing polyisocyanate, anurethodione group/isocyanurate group containing polyisocyanate, anurethane group containing polyisocyanate, an allophanate groupcontaining polyisocyanate, a biuret group containing polyisocyanate, acarbodiimide group containing polyisocyanate, and an uretodione groupcontaining polyisocyanate, each of which contains 1,6-hexamethylenediisocyanate and/or isophorone diisocyanate as a raw material; and aself-emulsifiable polyisocyanate obtained by reacting a hydrophilicsurfactant having at least one active hydrogen group which can reactwith an isocyanate group or polyethylene ether alcohol containing atleast three poly-ethylene oxide units with fatty acid ester in which thesum of the number of carbons of fatty acid and a hydroxyl containingcompound as raw materials is 8 or more and which has at least one activehydrogen group which can react with an isocyanate group. In addition tothe above, an urethane group-containing polyisocyanate obtained byreaction between 1,6-hexamethylenediisocyanate and/or an isophoronediisocyanate and an active hydrogen group-containing compound orpolyisocyanate obtained by an allophanatization reaction,carbodiimidization reaction, uretodionization reaction, andbiuretization reaction of these diisocyanate compounds can be mentioned.

Examples of suitable crosslinking agents containing an aldehyde arewaterdispersed or waterdispersible or water-soluble phenol formaldehyderesins, amino formaldehyde resins or combinations thereof.

Phenol formaldehyde crosslinking agents include, but are not limited to,reaction products of aldehydes with phenols. Preferred aldehdydes butnot exclusive are formaldehyde and acetaldehyde. A large variety ofphenols can be used such as but not exclusive phenol, cresol,p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol,cyclopentylphenol, cresylic acid, bisphenol-A, bisphenol-F and the likeand combinations thereof. Also acid functional phenols could be used inmaking phenol formaldehyde resins. The crosslinkers can be unetherifiedor etherified with alcohols or polyols. These phenol formaldehyde resinsmay be soluble or self-emulsifiable in water or can be stabilized by useof colloid stabilizers such as polyvinyl alcohol.

Amino formaldehyde crosslinking agents include, but are not limited to,reaction products of aldehydes with amino or amido group containingmolecules. Exemplary aldehydes include, but are not limited to,formaldehyde and acetaldehyde. A large variety of amino or amido groupcontaining molecules can be used such as but not exclusive urea,melamine, benzoguanamine, acetoguanamine, glycoluril and the like.Suitable amino crosslinking resins include melamine-formaldehyde,urea-formaldehyde, benzoguanamine-formaldehyde,acetoguanamine-formaldehyde, glycoluril-formaldehyde resins. Also themethylol groups of an amino formaldehyde resin can be partially or fullyetherified with at least one of the groups of monohydric aliphaticalcohols such as methanol and/or n-butanol. These amino formaldehyderesins may be soluble or self-emulsifiable in water or can be stabilizedby use of colloid stabilizers such as polyvinyl alcohol can be used tostabilize the amino formaldehyde dispersions.

Commercially available amino-formaldehyde resins which are water solubleor water dispersible and useful for the instant purpose include Cymel™301, Cymel™ 303, Cymel™ 370, and Cymel™ 373 (all being products of CytecSurface Specialties, Brussels, Belgium). Other aldehydes used to reactwith the amino compound to form the resinous material are crotonicaldehyde, acrolein, or compounds which generate aldehydes, such ashexamethylene-tetramine, paraldehyde, and the like.

Another class of crosslinking agents for carboxylic acid groups arewater-soluble hydroxyalkylamide crosslinkers such asBis(N,N′-dihydroxyethyl)adipamide and the like. Such compounds arecommercially available under the tradename of PRIMID™ crosslinker resinsfrom EMS-PRIMID in Switzerland, for example PRIMID™ XL-522, PRIMID™SF-4510 and PRIMID™ QM-1260

The one or more crosslinking agents may be added to the aqueousdispersion as part of the aqueous dispersion formulation process; or inthe alternative, the one or more crosslinking agents may be added to theaqueous dispersion post dispersion formulation process.

In one embodiment, depending on the type of food or beverage which is tobe contained in a coated container, and on required coating propertiesit may be beneficial to combine several crosslinkers or somecrosslinkers may be more suited than others. Some crosslinkers may notbe suited for all applications. Some crosslinkers may require theaddition of catalysts for proper cure.

Crosslinkers will help to build thermoset networks, which is indicatedby higher values of MEK Double Rubs compared to an identical formulationnot containing the crosslinker.

Forming the Dispersion

The aqueous dispersion can be formed by any number of methods recognizedby those having skill in the art. Dispersion equipment can be operatedin batch, semi-batch, or continuous mode. Examples of mixers includerotor-stator, microfluidizer, high pressure homogenizer, ultrasonic,impinging jet, Cowles™ blade, planetary mixers, and melt kneadingdevices such as extruders.

In one embodiment, one or more first polyesters, one or more stabilizingagents comprising a second polyester are melt-kneaded in an extruderalong with water and optionally one or more neutralizing agents, such asammonia, potassium hydroxide, amine, or a combination of two or more, toform a dispersion. In another embodiment, one or more first polyesters,one or more stabilizing agents comprising a second polyester arecompounded, and then melt-kneaded in an extruder in the presence ofwater, and optionally one or more neutralizing agents thereby forming adispersion. In some embodiments, the dispersion is first diluted tocontain from 1 to 20 percent, e.g., 1 to 5 percent or 1 to 3 percent, byweight of water, and then, subsequently, further diluted to comprisefrom 15 to 90 percent by weight of water, based on the weight ofdispersion. In one embodiment, further dilution may be accomplished viaa solvent. In one embodiment, the dispersion is free of any solvent.

Any melt-kneading means known in the art may be used. In someembodiments, a kneader, a BANBURY® mixer, single-screw extruder, or amulti-screw extruder, e.g. a twin screw extruder, melt pump inconnection with a rotor stator is used. A process for producing thedispersions in accordance with the present invention is not particularlylimited. For example, an extruder, in certain embodiments, for example,a twin screw extruder, is coupled to a back pressure regulator, meltpump, or gear pump. Exemplary embodiments also provide a base reservoirand an initial water reservoir, each of which includes a pump. Desiredamounts of base and initial water are provided from the base reservoirand the initial water reservoir, respectively. Any suitable pump may beused, but in some embodiments, for example, a pump that provides a flowof about 150 cc/min at a pressure of 240 bar is used to provide the baseand the initial water to the extruder. In other embodiments, a liquidinjection pump provides a flow of 300 cc/min at 200 bar or 600 cc/min at133 bar. In some embodiments, the base and initial water are preheatedin a preheater.

One or more first polyesters, in the form of, for example, pellets,powder, or flakes, are fed from the feeder to an inlet of the extruderwhere the resin is melted or compounded. One or more additionalcomponents may optionally be fed simultaneously with one or more firstpolyesters into the extruder via the feeder; or in the alternative, oneor more additional components may be compounded into one or more firstpolyesters, and then fed into the extruder via the feeder. In thealternative, additional one or more additional components may optionallyfurther be metered via an inlet prior to the emulsification zone intothe molten compound comprising one or more first polyesters. In someembodiments, the stabilizing agent comprising a second polyester isadded to one or more first polyesters through and along with the firstpolyesters and in other embodiments, the stabilizing agent comprising asecond polyester is provided separately to the twin screw extruder. Theresin melt is then delivered from the mix and convey zone to anemulsification zone of the extruder where the initial amount of waterand base from the water and base reservoirs are added through an inlet.In some embodiments, stabilizing agent comprising a second polyester maybe added additionally or exclusively to the water stream. In someembodiments, further dilution water may be added via water inlet fromwater reservoir in a dilution and cooling zone of the extruder.Typically, the dispersion is diluted to at least 30 weight percent waterin the cooling zone. In addition, the diluted mixture may be diluted anynumber of times until the desired dilution level is achieved. In someembodiments, the dispersion is further cooled after exiting the extruderby the use of a suitable heat exchanger. In other embodiments, water isnot added into the twin screw extruder but rather to a stream containingthe resin melt after the melt has exited from the extruder. In thismanner, steam pressure build-up in the extruder is eliminated and thedispersion is formed in a secondary mixing device such as a rotor statormixer.

In another embodiment, the aqueous dispersion can be formed in acontinuous high shear mixer without the use of a melt kneading extruder.In this embodiment, the first stream comprising one or more liquid ormolten first polyesters is supplied to a continuous high shear mixerfrom a suitable liquid pump for example, a syringe pump, gear pump, orprogressive cavity pump. The first stream is flowed through a firstconduit and merged continuously with a second stream containing acontinuous aqueous phase that is flowed through a second conduit. Thefirst and second streams are merged into a disperser in the presence ofa stabilizing agent comprising a second polyester with optionalneutralizing agent. The agents can be added to either the first orsecond stream, or as a separate stream. A third stream comprising watercan be added downstream from the disperser. The flow rates of thestreams are adjusted to achieve a dispersion having the desired amountof polymer phase and percent solids. The disperser can be any one of anumber of continuous inline mixers, for example, an IKA high-shearmixer, Oakes rotor stator mixer, Ross mixer, Silverson mixer, orcentrifugal pump. The rpm setting of the disperser can be used to helpcontrol the particle size of the dispersed hydrophobic phase in thedispersion. The system can be heated to provide the polymer andneutralizer components at a suitable viscosity for pumping. Steamformation is reduced by controlling the pressure through the use of abackpressure regulator, gear pump, metering pump, or other suitabledevice near the exit of the process. In some embodiments, the dispersionis further cooled after exiting the disperser by the use of a suitableheat exchanger.

In another embodiment, the aqueous dispersion can be formed in a batchor semi-batch high shear mixer where the mixer may, for example, bedisposed within a pressurized tank to, for example, reduce steamformation. All or at least a portion of the dispersion is removed fromthe tank during processing, and optionally cooled by the use of asuitable heat exchanger.

During the preparation of the aqueous dispersion, optionally one or morefillers; optionally one or more additives such as catalysts, wettingagents, defoamers, flow agents, release agents, slip agents,anti-blocking agents, additives to mask sulfur staining, pigmentwetting/dispersion agents, anti-settling agents, UV stabilizers,adhesion promoters; optionally one or more lubricants such as fatty acidester wax, silicon-based wax, fluorine-based wax, polyethylene or anyother similar polyolefin wax, carnauba wax, lanolin wax or the like;optionally one or more corrosion inhibitors such as aluminum, and zinc:optionally one or more pigments, e.g. titanium dioxide, mica, calciumcarbonate, barium sulfate, silica, zinc oxide, milled glass, aluminumtrihydrate, talc, antimony trioxide, fly ash, and clay or the like;optionally one or more dyes; optionally one or more co-solvents, e.g.glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate,alcohols, mineral spirits, and benzoate esters or the like; optionallyone or more dispersants, e.g. aminoalcohols, and polycarboxylates;optionally one or more surfactants; optionally one or more defoamers;optionally one or more preservatives, e.g. biocides, mildewcides,fungicides, algaecides, and combinations thereof; optionally one or morethickeners, e.g. cellulosic based thickeners such as hydroxyethylcellulose, hydrophobically modified alkali soluble emulsions (HASEthickeners such as UCAR POLYPHOBE TR-116) and hydrophobically modifiedethoxylated urethane thickeners (HEUR); or optionally one or moreadditional neutralizing agents, e.g. hydroxides, amines, ammonia, andcarbonates may be added to the aqueous dispersion formulation; or in thealternative, may be added to the dispersion post dispersion formulationprocess.

During the preparation of the aqueous dispersion, one or morecrosslinking agents may also be added to the aqueous dispersionformulation; or in the alternative, may be added to the dispersion postdispersion formulation process.

Optionally during the dispersion of the one or more first polyesters,another polymer dispersion or emulsion may be used as a portion of theaqueous phase of the dispersion. Examples include, but are not limitedto, acrylic, epoxy, polyester, polyurethane, polyolefin, polyamide,alkyd, and the like containing dispersions, emulsions, suspensions,colloidal suspensions.

In one embodiment, the method for producing the inventive aqueousdispersion comprises the steps of: (1) selecting one or more firstpolyesters having an acid number in the range of from less than 15, forexample less than 10, or in the alternative less than 5; (2) selectingone or more stabilizing agents comprising at least one second polyesterhaving an acid number equal to or greater than 15, for example greaterthan 20; (3) selecting one or more neutralizing agents; (4)melt-blending said one or more first polyesters, one or more stabilizingagents in the presence of water and one or more neutralizing agents; (4)thereby producing an aqueous dispersion having a solid content of 10 to74 percent, based on the total weight of the dispersion.

Coating Applications and Forming Coated Containers or Closure Devices

The aqueous dispersion and/or coating composition derived therefrom maybe used on any suitable substrate including, but not limited to metal,wood, paper, plastic, leather, glass, concrete, and the like. In oneembodiment the aqueous dispersion and/or coating derived therefrom maybe used, for example, in container, e.g. can, coating application, orclosure device coating application. Such coated container devicesinclude, but are not limited to, cans such as beverage cans, food cans;aerosol containers such as those for non-food products, e.g. hair spray,hair dye, or color spray lacquers; drums; kegs; pails; decorative tins;open trays; tubes, bottles, monoblocs, and the like. The coated articlessuch as closure devices include, but are not limited to, caps, lids suchas thin aluminum foil based lids for yogurt and butter containers, orcrown corks; closures for glass jars and bottles such as roll-onclosures, vacuum closures, pilfer-proof closures, easy peel lids for canclosures, and easy open end or conventional ends for cans. Cans may be 2piece cans or 3 piece cans. Beverage cans include, but are not limitedto, beer cans, carbonated soft drink cans, energy drink cans, isotonicdrink cans, water cans, juice cans, tea cans, coffee cans, milk cans,and the like. Food cans, include, but are not limited to, vegetablecans, fruit cans, meat cans, soup cans, ready meal cans, fish cans,edible oil cans, sauce cans and the like. Such cans may have any shapes;for example, such can may have a cylindrical shape, cubical, spherical,semi-spherical, bottle shape, elongated cubical shape, shallow or tallshape, round or rectangular shape or any other suitable shape. Thecoated articles such as container devices according to the instantinvention may be formed via any conventional method. For example, thecoated container device may be formed via stamping, drawing, redrawing,wall ironing, bending, beading, embossing, debossing, flanging, necking,stretching, blow-stretching and any other suitable conventional method.Such methods are generally known to those having ordinary skill in theart. The aqueous dispersion and/or coating composition derived therefrommay, for example, be applied to a substrate, e.g. metal sheet or metalfoil, and then the coated substrate may be formed into a coatedcontainer device or a coated closure device. In the alternative, asubstrate may be formed into a container device or a closure device, andthen the container device or the closure device is coated with one ormore aqueous dispersions and/or coating composition derived therefrom toform the coated container device or coated closure device. The coatingmay be applied via any method; for example, via roller coating, spraycoating, powder coating, dip coating, electrodeposition coating,printing, wash coating, flow coating, curtain coating.

The substrate comprises one or more metals including, but not limitedto, aluminum and aluminum alloys, electrolytic tinplate cold rolled lowcarbon mild steel (“ETP”), electrolytic chromium/chromium oxide coatedcold rolled low carbon mild steel (ECCS), and any other pre-treatedsteel, or one or more polymers such as one or more polyolefins, e.g.polyethylene and/or polypropylene. Pretreatment may include, but is notlimited to, treatment with phosphoric acid, zirconium phosphate,chromium phosphate, and the like as well as silanes for reasons such asprimary corrosion protection and improved adhesion. The substrate maycomprise a sheet, strip or a coil. The substrate may comprise one ormore layers, and each layer may have a thickness in the range of from0.01 μm to 2 mm; for example, from 0.01 μm to 1.5 mm; or in thealternative, from 0.01 μm to 1 mm; or in the alternative, from 0.01 μmto 0.5 mm; or in the alternative, from 0.01 μm to 0.2 mm; or in thealternative, from 0.01 μm to 0.1 mm or in the alternative, from 0.01 μmto 100 μm; or in the alternative, from 0.01 μm to 50 μm; or in thealternative, from 1 μm to 50 μm; or in the alternative, from 1 μm to 15μm. The substrate may be pre-coated with one or more pre-coatingcompositions. Such pre-coating compositions may optionally furtherinclude, but are not limited to, one or more resin binders, one or moreresin crosslinkers, one or more solvents, one or more additives, and oneor more pigments. Exemplary resin binders include, but are not limitedto, epoxy, polyester, polyvinyl chloride containing organosols/vinyls,phenolic, alkyd, oleoresin, acrylic resin, and the like. Exemplarycrosslinkers include, but are not limited to, phenol-formaldehyderesins; amino-formaldehyde resins including but not limited tourea-formaldehyde, melamine formaldehyde, benzoguanamine formaldehyde;anhydride resins, blocked isocyanate resins and epoxy groups containingresins, including but not limited to, epoxy resins, epoxy groupscontaining polyesters, acrylic resins, vinyl resins or the like.Exemplary solvents and thinners include, but are not limited to, glycolethers, alcohols, aromatics, e.g. aromatic hydrocarbons, white spirit,branched ketones and esters. Exemplary additives include, but are notlimited to, catalysts, lubricants, wetting agents, defoamers, flowagents, release agents, slip agents, anti-blocking agents, additives tomask sulfur staining, pigment wetting/dispersion agents, anti-settlingagents, UV stabilizers, adhesion promoters. Pigments include, but arenot limited to titanium dioxide, zinc oxide, aluminum oxide, zinc andaluminum. The substrate may also be pre-coated with one or morepre-coated laminate compositions. Such compositions may, for example,include polyethylene, polypropylene, or polyester compositions, and maybe applied either as a film via film lamination process ormelt-extrusion coating process onto the metal surface.

The one or more aqueous dispersions and/or coating composition derivedtherefrom applied to the at least one surface of the substrate may bedried via any conventional drying method. Such conventional dryingmethods include but, are not limited to, air drying, convection ovendrying, hot air drying, and/or infrared oven drying. During the dryingprocess, crosslinking of one or more base polymers, stabilizing agents,or combinations thereof, involving one or more the crosslinking agents,may occur. Additional cure might occur by radiation cure, e.g.electron-beam cure. The one or more aqueous dispersions and/or coatingcomposition derived therefrom applied to the at least one surface of thesubstrate may be dried at any temperature; for example, it may be driedat a temperature in the range of equal or greater than the melting pointtemperature of the first polyester; or in the alternative, it may bedried at a temperature in the range of less than the melting point ofthe stabilizing agent comprising a second polyester. The one or moreaqueous dispersions and/or coating composition derived therefrom appliedto the at least one surface of the substrate may be dried at atemperature in the range of about 60° F. (15.5° C.) to about 700° F.(371° C.) for a period of less than about 40 minutes, for example, lessthan 20 minutes, or less than 10 minutes, or less than 5 minutes, orless than 2 minutes, or less than 1 minute, or less than 20 seconds. Allindividual values and subranges from about 60° F. (15.5° C.) to about700° F. (371° C.) are included herein and disclosed herein; for example,the one or more aqueous dispersions and/or coating composition derivedtherefrom applied to the at least one surface of the substrate may bedried at a temperature in the range of about 60° F. (15.5° C.) to about500° F. (260° C.) for a period of less than about 40 minutes, forexample, less than 20 minutes, or less than 10 minutes, or less than 5minutes, or less than 2 minutes, or less than 1 minute, or in thealternative, the one or more aqueous dispersions and/or coatingcomposition derived therefrom applied to the at least one surface of thesubstrate may be dried at a temperature in the range of about 60° F.(15.5° C.) to about 450° F. (232.2° C.) for a period of less than about40 minutes, for example, less than 20 minutes, or less than 10 minutes,or less than 5 minutes, or less than 2 minutes, or less than 1 minute.The temperature of the one or more aqueous dispersions and/or coatingcomposition derived therefrom applied to the at least one surface of thesubstrate may be raised to a temperature in the range of equal orgreater than the melting point temperature of the base polymer for aperiod of less than about 40 minutes. All individual values andsubranges from less than about 40 minutes are included herein anddisclosed herein; for example, the temperature of the one or moreaqueous dispersions and/or coating composition derived therefrom appliedto the at least one surface of the substrate may be raised to atemperature in the range of equal or greater than the melting pointtemperature of the first polyester for a period of less than about 20minutes, or in the alternative, the temperature of the one or moreaqueous dispersions applied and/or coating composition derived therefromto the at least one surface of the substrate may be raised to atemperature in the range of equal or greater than the melting pointtemperature of the first polyester for a period of less than about 5minutes, or in another alternative, the temperature of the one or moreaqueous dispersions and/or coating composition derived therefrom appliedto the at least one surface of the substrate may be raised to atemperature in the range of equal or greater than the melting pointtemperature of the first polyester for a period in the range of about0.5 to 300 seconds. In another alternative, the temperature of the oneor more aqueous dispersions and/or coating composition derived therefromapplied to the at least one surface of the substrate may be raised to atemperature in the range of less than the melting point temperature ofthe first polyester for a period of less than 40 minutes. All individualvalues and subranges from less than about 40 minutes are included hereinand disclosed herein; for example, the temperature of the one or moreaqueous dispersions and/or coating composition derived therefrom appliedto the at least one surface of the substrate may be raised to atemperature in the range of less than the melting point temperature ofthe first polyester for a period of less than about 20 minutes, or inthe alternative, the temperature of the one or more aqueous dispersionsand/or coating composition derived therefrom applied to the at least onesurface of the substrate may be raised to a temperature in the range ofless than the melting point temperature of the first polyester for aperiod of less than about 5 minutes, or in another alternative, thetemperature of the one or more aqueous dispersions applied and/orcoating composition derived therefrom to the at least one surface of thesubstrate may be raised to a temperature in the range of less than themelting point temperature of the first polyester for a period in therange of about 0.5 to 300 seconds.

The coated substrate may further be coated with one or more conventionalcoating compositions, or it may further be laminated to one or moreother layers. Such conventional coating compositions are generally knownto person of ordinary skill in the art, and they may include, but arenot limited to, epoxy resin coating compositions, acrylate based coatingcompositions, and polyester based coating compositions. The laminationprocess is generally known, and exemplary lamination layers may include,but are not limited to, polyester laminates, polyolefin based laminatessuch as polypropylene laminates.

The one or more aqueous dispersions and/or coating composition derivedtherefrom applied to at least one surface of a substrate, for example apre-coated substrate, as one or more crosslinked coating layers may havea cross cut adhesion, before retort, rating of at least 3B; for example,4 B or 5B, measured according to ASTM-D 3359-08. The one or more aqueousdispersions and/or coating composition derived therefrom applied to atleast one surface of a substrate as one or more crosslinked coatinglayers may have a wedge bend pass rating of at least 50 percent, forexample, at least 70 percent, or in the alternative, at least 80percent, or in the alternative, at least 90 percent, measured via aGardner “COVERALL” Bend Tester IG 1125.

The present disclosure further includes a waterborne polyolefin basedcoating layer that has improved features as compared to epoxy coatings.Epoxy coatings are useful in metal coatings for industrial applications(i.e. tank liner, coil, and pipe coatings, among others). For example,epoxy coatings, due to their highly cross-linked structure, have verygood acid and base resistance. Their highly cross-linked structure alsoresults in the epoxy coatings having a fairly rigid film. This rigidfilm, however, is not very durable (not very damage tolerant). Forexample, temperature cycling can impart significant stresses on epoxycoatings due to thermal expansion and contraction of both the epoxycoating and the underlying substrate (e.g., a metal tank). Eventually,the thermal expansion and contraction of these structures results infailure of the epoxy coating. Additionally, impacting the coating, orflexing the coating may result in failure of the film integrity.

The coating layer of the present disclosure, in contrast to epoxycoatings, provides for a coating layer having excellent acid and baseresistance, good adhesion to metal substrates, and good flexibility. Forexample, as provided in the Examples section, coating layers formed withthe coating composition of the present disclosure can survive numerousthermal cycles between 50° C. and −78.5° C., while maintaining goodadhesion to a metal substrate. As a result, coating layers formed fromthe coating compositions of the present disclosure might be useful as atank liner or as a pipe coating, among other uses.

As discussed herein, the coating composition of the present disclosureincludes 40 to 80 weight percent (wt. %) of a base polymer; 10 to 30 wt.% of a polymeric stabilizing agent; 5 to 15 wt. % of a polymericcoupling agent; 0 to 35 wt. % of a polymeric performance improvingagent; a neutralizing agent that partially or fully neutralize thepolymeric stabilizing agent; and a fluid medium, where the wt. % valuesare based on the total weight of the base polymer, the polymericcoupling agent, the polymeric stabilizing agent and, when present, thepolymeric performance improving agent (as used herein, this total weightof the base polymer, the polymeric coupling agent, the polymericstabilizing agent and, when present, the polymeric performance improvingagent may be referred to as the “solid content” of the coatingcomposition). The wt. % values provided herein are based on the totalweight of the solid content of the coating composition and sum to avalue of 100 wt. %.

As provided herein, advantages of the coating layer of the presentdisclosure are the combination of its acid and base resistance,flexibility and its adhesion to a variety of substrate surfaces (e.g.,metal, epoxy, polyurethane, cement surfaces, among others). Otheradvantages are discussed herein.

Base Polymer

The coating composition includes from 40 to 80 wt. % of a base polymer,where the wt. % is based on the total weight of the solid content, asdefined herein, of the coating composition. All individual values andsub-ranges from 40 to 80 wt. % are included herein and disclosed herein;for example, the wt. % can be from a lower limit of 40, 45 or 50 wt. %to an upper limit of 70, 75, or 80 wt. %. For example, the coatingcomposition may comprise from 40 to 75 wt. %, or from 40 to 70 wt. %, orfrom 45 to 80 wt. %, or from 45 to 75 wt. %, or from 45 to 70 wt. %, orfrom 50 to 80 wt. %, or from 50 to 75 wt. %, or from 50 to 70 wt. % ofthe base polymer, based on the total weight of the solid content of thecoating composition. The coating composition can include at least one ormore of the base polymers. For example, the coating composition caninclude two or more base polymers, as discussed herein. So, as usedherein “a base polymer” or “the base polymer” can be substituted with“two or more base polymers.”

The base polymer can be selected from the group consisting of anon-functionalized ethylene polymer, a non-functionalized propylenepolymer, a non-functionalized propylene/ethylene copolymer, andcombinations thereof. For example, the base polymer may include two ormore of the non-functionalized polymers discussed herein. As usedherein, “non-functionalized” means the absence of a reactive polar groupon the polymer.

The non-functionalized ethylene polymer can be selected from the groupconsisting of polyethylene, an ethylene-copolymer and a combinationthereof. Examples of the ethylene-copolymer can includenon-functionalized propylene/ethylene copolymers. The propylene/ethylenecopolymers may include propylene-ethylene alternating copolymers.Examples of such non-functionalized ethylene polymers andnon-functionalized propylene/ethylene copolymers include, but are notlimited to, VERSIFY™ DP-4000.01; VERSIFY™ 4200, VERSIFY™ 4000, VERSIFY™3200, VERSIFY™ 3000, and VERSIFY™ 3300, all available from The DowChemical Company; ENGAGE™ 8407 available from The Dow Chemical Company;INFUSE™ 9807 available from The Dow Chemical Company; Vistamaxx™propylene-based elastomers (available from ExxonMobil Chemical);commercially available high density polyethylenes such as, but are notlimited to, DMDA-8007 NT 7 (Melt Index 8.3, Density 0.965), DMDC-8910 NT7 (Melt Index 10, Density 0.943), DMDA-1210 NT 7 (Melt Index 10, Density0.952), HDPE 17450N (Melt Index 17, Density 0.950), DMDA-8920 NT 7 (MeltIndex 20, Density 0.954), DMDA 8940 NT 7 (Melt Index 44, Density 0.951),DMDA-8950 NT 7 (Melt Index 50, Density 0.942), DMDA-8965-NT 7 (MeltIndex 66, Density 0.952), DMDA-8940 HDPE (Melt Index of approximately40-48 g/10 min), all available from The Dow Chemical Company.

Exemplary non-functionalized ethylene polymers can also includehomogeneous polymers, as for example described in U.S. Pat. No.3,645,992; high density polyethylene (HDPE), as for example described inU.S. Pat. No. 4,076,698; heterogeneously branched linear low densitypolyethylene (LLDPE); heterogeneously branched ultra-low linear densitypolyethylene (ULDPE); homogeneously branched, linearethylene/alpha-olefin copolymers; homogeneously branched, substantiallylinear ethylene/alpha-olefin polymers, which can be prepared, forexample, by processes disclosed in U.S. Pat. Nos. 5,272,236 and5,278,272, the disclosures of which are incorporated herein byreference; and high pressure, free radical polymerized ethylene polymersand copolymers such as low density polyethylene (LDPE) or ethylene vinylacetate polymers (EVA). The non-functionalized ethylene polymer has acrystalline melting point of 100° C. to 230° C. Other values arepossible, where the crystalline melting point is measured by calorimetrymeasurements.

Examples of the non-functionalized propylene polymer can include, butare not limited to, 6D43 Polypropylene (available from Braskem).Generally the non-functionalized propylene polymer can be characterizedas having substantially isotactic propylene sequences. “Substantiallyisotactic propylene sequences” means that the sequences have anisotactic triad (mm) measured by ¹³C NMR of greater than about 0.85; inthe alternative, greater than about 0.90; in another alternative,greater than about 0.92; and in another alternative, greater than about0.93. Isotactic triads are well-known in the art and are described in,for example, U.S. Pat. No. 5,504,172 and International Publication No.WO 00/01745, which refers to the isotactic sequence in terms of a triadunit in the copolymer molecular chain determined by ¹³C NMR spectra.

Other examples of the base polymer include, but are not limited to,ethylene ethyl acrylate copolymer, ethylene methyl methacrylate,ethylene butyl acrylate, and combinations thereof.

The base polymer can have a density of at least 0.88 grams/mole asmeasured by ASTM D972. Specific examples include, but are not limitedto, 0.88 grams/mole to 1.0 grams/mole or from 0.88 grams/mole to 0.98grams/mole. The base polymer has a crystalline melting point of at least100° C. as measured using Differential Scanning calorimetry (DSC).

Polymeric Stabilizing Agent

The coating composition further includes a polymeric stabilizing agentto promote the formation of a stable dispersion during the formation ofthe coating composition. The polymeric stabilizing agent may preferablybe an external stabilizing agent. The coating composition includes 10 to30 wt. % of the polymeric stabilizing agent, based on the total weightof the solid content, as defined herein, of the coating composition. Thecoating composition can also include 5 to 50 wt. % of the polymericstabilizing agent, based on the total weight of the solid content, asdefined herein, of the coating composition. All individual values andsubranges from 5 to 50 wt. % are included herein and disclosed herein;for example, the wt. % can be from a lower limit of 5, 10 or 15 wt. % toan upper limit of 30, 40 or 50 wt. %. For example, the coatingcomposition may comprise from 5 to 40 wt. %, or from 5 to 30 wt. %, orfrom 10 to 30 wt. %, or from 10 to 40 wt. %, or from 10 to 50 wt. %, orfrom 15 to 30 wt. %, or from 15 to 40 wt. % or from 15 to 50 wt % of thepolymeric stabilizing agent, based on the total weight of the solidcontent of the coating composition. The coating composition may alsocomprise from 20 to 24 wt. % of the polymeric stabilizing agent, basedon the total weight of the solid content of the coating composition.

The polymeric stabilizing agent can have an acid number of equal to orgreater than 100, greater than 110, or for a number of embodimentsgreater than 140. The polymeric stabilizing agent can be a polarpolymer, e.g., including a polar group as either a comonomer or graftedmonomer. In some embodiments, the polymeric stabilizing agent caninclude one or more polar polyolefins, e.g., having a polar group aseither a comonomer or grafted monomer. Acid Number values (the amount ofKOH in mg KOH/g polymer required to neutralize acid functionality whenmeasured by titration) can be measured according to ASTM D-1386.

Examples of polymeric stabilizing agents include, but are not limitedto, ethylene-acrylic acid and ethylene-methacrylic acid copolymershaving a functionality in a range of 10 wt. % to 25 wt. %. Functionalityvalues (the amount of functional monomer expressed as weight percent ofthe resin) can be determined by ASTM D 4094 or equivalent. Examples ofsuch polymeric stabilizing agents include those available under thetrademarks PRIMACOR™, such as PRIMACOR™ 5980i or PRIMACOR™ 5990i, bothcommercially available from The Dow Chemical Company; NUCREL™,commercially available from E.I. DuPont de Nemours; and ESCOR™,commercially available from ExxonMobil Chemical Company and described inU.S. Pat. Nos. 4,599,392, 4,988,781, and 5,938,437, each of which isincorporated herein by reference in its entirety. Otherethylene-carboxylic acid copolymer may also be used. Those havingordinary skill in the art will recognize that a number of other usefulpolymers may also be used. Examples include products under the tradename CERAMER from Baker-Hughes Company, such as CERAMER 1608; and PA-18polyanhydride copolymer from Chevron-Phillips Company.

Polymeric Coupling Agent

The coating composition further includes a polymeric coupling agent. Thepolymeric coupling agent can help in formation of the coatingcomposition, e.g., help provide a more uniform dispersion, and/orimprove properties of a cured coating composition. The coatingcomposition includes 5 to 15 wt. % of the polymeric coupling agent,based on the total weight of the solid content, as defined herein, ofthe coating composition. All individual values and subranges from 5 to15 wt. % are included herein and disclosed herein; for example, the wt.% can be from a lower limit of 5 or 6 wt. % to an upper limit of 8, 9 or15 wt. %. For example, the coating composition may comprise from 5 to 8wt. %, or from 5 to 9 wt. %, or from 5 to 15 wt. %, or from 6 to 8 wt.%, or from 6 to 9 wt. %, or from 6 to 15 wt. % of the polymeric couplingagent, based on the total weight of the solid content of the coatingcomposition.

The polymeric coupling agent can have a melt viscosity of less than80000 centipoise (cP) at 150° C., less than 40000 cP at 150° C., lessthan 20000 cP at 150° C., or for a number of embodiments, less than10000 at 150° C. Melt viscosity can be determined by DIN 53019 or ASTMD-1986, e.g., measurement of wax viscosity using a Brookfield rotationalviscometer. For a number of embodiments, the polymeric coupling agentcan have an acid number less than 100.

The polymeric coupling agent can include a modified, e.g.,functionalized, polymer, such as a functionalized polyolefin. Forexample, the polymeric coupling agent can be selected from the groupconsisting of a functionalized polypropylene, a functionalizedpolyethylene homopolymer, a copolymer that has been modified withcarboxylic acid groups, a copolymer that has been modified withanhydride groups and a combination thereof. The polymeric coupling agentcan also be selected from a low molecular weight compound havingreactive polar groups. Examples of the polymeric coupling agent include,but are not limited to modified olefin polymers. The modified olefinpolymers can include graft copolymers and/or block copolymers, such aspropylene-maleic anhydride graft copolymer. Examples of groups that canmodify the polymer include, but are not limited to, acid anhydrides,carboxylic acids, carboxylic acid derivatives, primary and secondaryamines, hydroxyl compounds, oxazoline and epoxides, and ionic compounds,and combinations thereof.

Specific examples of the groups that can modify the polymer include, butare not limited to, unsaturated cyclic anhydrides and their aliphaticdiesters, and the diacid derivatives. For example, maleic anhydride andcompounds selected from C₁-C₁₀ linear and branched dialkyl maleates,C₁-C₁₀ linear and branched dialkyl fumarates, itaconic anhydride, C₁-C₁₀linear and branched itaconic acid dialkyl esters, maleic acid, fumaricacid, itaconic acid, and combinations thereof. Commercially availableexamples of polymeric coupling agents include, but are not limited to,polymers available under the trade name LICOCENE®, or LICOLUBE®, fromClariant Corporation, such as LICOCENE® 6452 (e.g., LICOCENE® PP MA6452) and LICOCENE® 4351 (e.g., LICOCENE® PE MA 4351); polymers underthe trade name A-C™ Performance Additives from Honeywell Corporation,such as AC575™ which is an ethylene maleic anhydride copolymer, andAC-392™ and AC395™ which are high density oxidized polyethylene;products under the trade name CERAMER from Baker-Hughes Company;EXXELOR™ from ExxonMobil Chemical Company; and Epolene from WestlakeChemical Company.

Polymeric Performance Improving Agent

The coating composition further includes a polymeric performanceimproving agent. The polymeric performance improving agent can help tosimultaneously provide particular performance characteristics, such asparticular appearance properties and particular mechanical and chemicalresistance properties for a coated article, which are desirable for somecoating applications. The coating composition includes 0 to 35 wt. % ofthe polymeric performance improving agent, based on the total weight ofthe solid content, as defined herein, of the coating composition. Allindividual values and subranges from 0 to 35 wt. % are included hereinand disclosed herein; for example, the wt. % can be from a lower limitof 0, 5 or 10 wt. % to an upper limit of 15, 20, or 35 wt. %. Forexample, the coating composition may comprise from 0 to 15 wt. %, orfrom 0 to 20 wt. %, or from 0 to 35 wt. %, or from 5 to 15 wt. %, orfrom 5 to 20 wt. %, or from 5 to 35 wt. %, or from 10 to 15 wt %, orfrom 10 to 20 wt. % or from 10 to 35 wt. % of the polymeric performanceimproving agent, based on the total weight of the solid content of thecoating composition.

The polymeric performance improving agent can have an acid number ofless than 60, less than 50, or for a number of embodiments, less than42. Acid number can be determined by ASTM D-1386, for example. Acidnumber can refer to an amount of KOH in mgKOH/g polymer required toneutralize acid functionality when measured by titration. Alternativelythe percent functionality can be determined by Fourier TransformInfrared Spectrosdopy (FTIR).

The polymeric performance improving agent can have a melt index value ofless than 100, less than 70, or for a number of embodiments, less than30. Melt index values can be determined by ASTM D-1238, for example. Asused herein, melt index values can be defined as the amount of polymermelt passing in dg/min (or g/10 min) through a heated syringe with aplunger load, e.g., at 190° C. and 2.16 kg load for polyethylene basedpolymer and at 230° C. and 2.16 kg for polypropylene based polymer.

Embodiments of the present disclosure provide that the polymericperformance improving agent can be selected from the group consisting offunctionalized polyethylene, functionalized polypropylene,non-functionalized copolymer of ethylene and propylene and a combinationthereof. Examples of the functionalized polyethylene include, but arenot limited to, maleic anhydride functionalized polyethylene, such ashigh density polyethylene. Maleic anhydride functionalized polyethylenecopolymers, terpolymers and blends may also be used. Maleic anhydridefunctionality can be incorporated into the polymer by grafting or otherreaction methods. When grafting, the level of maleic anhydrideincorporation is typically below 3 percent by weight based on the weightof the polymer. Examples of commercially available maleic anhydridefunctionalized polyethylene include those available under the tradenameAMPLIFY™ available from The Dow Chemical Company, such as AMPLIFY™GR-204, among others. Amplify GR-204 is 2,5-Furandione modifiedethylene/hexene-1 polymer. Other examples of maleic anhydridefunctionalized polyethylene are available under the tradename FUSABOND™available from E.I. du Pont de Nemours and Company such as FUSABOND™E-100, FUSABOND™ E-158, FUSABOND™ E265, FUSABOND™ E528, FUSABOND™ E-589,FUSABOND™ M-603, among others; Other maleic anhydride graftedpolyethylene polymers, copolymers, and terpolymers may include POLYBOND™available from Chemtura, such as POLYBOND™ 3009 and POLYBOND™ 3029,among others; OREVAC™ available from ARKEMA, such as OREVAC™ 18510P,among others; PLEXAR™ from Lyondell Chemical Company, such as PLEXAR™PX-2049; also grades available under the tradename YPAREX from B.V. DSMEngineering Plastics, such as YPAREX 8305; and polymers available underthe tradename EXXELOR™, such as Exxelor™ PE 1040. Other examples includeLOTADER 4210 a random terpolymer of ethylene, acrylic ester and maleicanhydride available from ARKEMA. Additional polyethylene functionalizedwith glycidyl methacrylate may be used. Other examples of the polymericperformance improving agent include non-functionalized polymersavailable under the trade name VERSIFY™, such as VERSIFY™ 4200, VERSIFY™4000, VERSIFY™ 3200, VERSIFY™ 3000, and VERSIFY™ 3300, all availablefrom The Dow Chemical Company.

Neutralizing Agent

The acid groups of the polymeric stabilizing agent may be partially orfully neutralized with a neutralizing agent. In certain embodiments,neutralization of the stabilizing agent may be from 25 to 200 percent ona molar basis; or in the alternative, it may be from 50 to 165 percenton a molar basis; or in the alternative, it may be from 50 to 150percent on a molar basis; or in the alternative, it may be from 50 to120 percent on a molar basis.

Examples of suitable neutralizing agents include a volatile base. Asused herein a volatile base is a base that can be evaporated (conversionof a liquid to a gas or vapor) at a temperature in a range from 100° C.to 200° C. at a pressure in a range of 1 atmosphere. Examples of such avolatile base include, but are not limited to, N,N-dimethylethanolamine,ammonia, hydrazine, methylamine, ethylamine, diethylamine,triethylamine, isobutylamine, N,N-diisopropylethylamine, morpholine,piperazine, ethylenediamine, and 1,4-diazabicyclo[2.2.2]octane).Evaporation of the volatile base upon formation of the coating layerresults in the functional groups of the polymeric stabilizing agentreverting to the acid form where it can help to promote adhesion of thecoating layer to the surface of the substrate.

Other neutralizing agents can include, for example, an amine such asmonoethanolamine, or 2-amino-2-methyl-1-propanol (AMP). Amines useful inembodiments disclosed herein may include diethanolamine,triethanolamine, and TRIS AMINO™ (each available from Angus), NEUTROL™TE (available from BASF), as well as triisopropanolamine anddiisopropanolamine (each available from The Dow Chemical Company). Otheruseful amines may include dimethylamine, trimethylamine,mono-n-propylamine, butylamine, dibutylamine, tributylamine, dimethylbenzyl amine, dimethyl n-propylamine, N-methanol amine,N-aminoethylethanolamine, N-methyldiethanolamine, monoisopropanolamine,N,N-dimethyl propanolamine, 2-amino-2-methyl-1-propanol,1,2-diaminopropane, tris(hydroxymethyl)-aminomethane, ethylenediamine,N,N,N′N′-tetrakis(2-hydroxylpropyl)ethylenediamine, 3-methoxypropylamine, imino bis-propyl amine, and the like. In some embodiments,mixtures of amines or mixtures of amines and surfactants may be used. Inone embodiment, the neutralizing agent may be a polymeric amine, e.g.diethylene triamine. Those having ordinary skill in the art willappreciate that the selection of an appropriate neutralizing agentdepends on the specific composition formulated, and that such a choiceis within the knowledge of those of ordinary skill in the art. In oneembodiment, amines with boiling points below 250° C. may be used as theneutralizing agents.

Fluid Medium

The coating composition further includes a fluid medium. The fluidmedium may be, for example, water; or in the alternative, the fluidmedium may be a mixture of water and one or more organic solvents, e.g.one or more water miscible solvents or one or more water immisciblesolvents, or combinations thereof. The coating composition of thepresent disclosure includes 15 to 99 percent by weight of fluid medium,based on the total weight of the coating composition. In particularembodiments, the fluid medium content may be in the range of from 30 to80, or in the alternative from 35 to 75, or in the alternative from 40to 70 percent by volume, based on the total weight of the coatingcomposition.

Fluid medium content of the coating composition may preferably becontrolled so that the solids content (base polymer(s), polymericstabilizing agent(s), polymeric coupling agent and optionally polymericperformance improving agent(s)) is from 15 percent to 99 percent byweight of the coating composition. In particular embodiments, the solidsrange may be from 15 percent to 85 percent by weight of the coatingcomposition. In other particular embodiments, the solids range may befrom 30 percent to 80 percent by weight of the coating composition. Inother particular embodiments, the solids range is from 35 percent to 75percent by weight of the coating composition. In certain otherembodiments, the solids range is from 40 percent to 70 percent by weightof the coating composition.

The coating composition of the present disclosure may optionally beblended with one or more cross-linkers such as those described in PCTPub. No. WO/2011/011707. These cross-linkers may be organic, orinorganic (i.e. zinc nanoparticles) in nature. The coating compositionof the present disclosure may also be optionally be blended with one ormore binder compositions such as acrylic latex, vinyl acrylic latex,styrene acrylic latex, vinyl acetate ethylene latex, and combinationsthereof; optionally one or more fillers; optionally one or moreadditives such as catalysts, wetting agents, defoamers, flow agents,release agents, slip agents, anti-blocking agents, additives to masksulfur staining, pigment wetting/dispersion agents, anti-settlingagents, UV stabilizers, adhesion promoters; optionally one or morelubricants such as fatty acid ester wax, silicon-based wax,fluorine-based wax, polyethylene or any other similar polyolefin wax,carnauba wax, lanolin wax or the like; optionally one or more corrosioninhibitors such as aluminum, and zinc: optionally one or more pigments,e.g. titanium dioxide, barium sulfate, mica, calcium carbonate, silica,zinc oxide, milled glass, aluminum trihydrate, talc, antimony trioxide,fly ash, and clay or the like; optionally one or more co-solvents, e.g.glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate,alcohols, mineral spirits, aromatic solvents and benzoate esters or thelike; optionally one or more dispersants, e.g. aminoalcohols, andpolycarboxylates; optionally one or more surfactants; optionally one ormore preservatives, e.g. biocides, mildewcides, fungicides, algaecides,and combinations thereof; optionally one or more thickeners, e.g.cellulosic based thickeners such as hydroxyethyl cellulose,hydrophobically modified alkali soluble emulsions (HASE thickeners suchas UCAR POLYPHOBE TR-116) and hydrophobically modified ethoxylatedurethane thickeners (HEUR); or optionally one or more additionalneutralizing agents, e.g. hydroxides, amines, ammonia, and carbonates;optionally one or more solvents or coalescing agents.

In addition, the coating composition may be blended with one or moredispersions, emulsions, suspensions, colloidal suspensions, and thelike.

The coating composition can be formed by any number of methodsrecognized by those having skill in the art. Dispersion equipment can beoperated in batch, semi-batch, or continuous mode. Examples of mixersused in the dispersion include rotor-stator, microfluidizer, highpressure homogenizer, ultrasonic, impinging jet, Cowles blade, planetarymixers, and melt kneading devices such as extruders.

In one embodiment, the base polymer and the polymeric stabilizing agentare melt-kneaded in an extruder along with the fluid medium (e.g.,water) and optionally the neutralizing agent to form a dispersion. Inanother embodiment, the base polymer and the polymeric stabilizing agentare compounded, and then melt-kneaded in an extruder in the presence ofthe fluid medium (e.g., water), and optionally the neutralizing agent,thereby forming a dispersion. In some embodiments, the dispersion isfirst diluted to contain 1 to 20%, e.g., 1 to 5% or 1 to 3%, by weightof the fluid medium and then, subsequently, further diluted to comprisegreater than 25% by weight of the fluid medium. In one embodiment,further dilution may be accomplished via water and/or a solvent asprovided herein.

Melt-kneading means known in the art may be used. In some embodiments, akneader, a BANBURY® mixer, single-screw extruder, or a multi-screwextruder, e.g. a twin screw extruder, is used. One example of a suitableextruder system is provided in PCT publication WO 2011/068525 entitled“Extruder Screw,” which is incorporated herein by reference.

A process for producing the coating composition in accordance with thepresent disclosure is not particularly limited. For example, anextruder, in certain embodiments, for example, a twin screw extruder, iscoupled to a back pressure regulator, melt pump, or gear pump. Exemplaryembodiments also provide a neutralizing agent reservoir and an initialfluid medium reservoir, each of which includes a pump. Desired amountsof neutralizing agent and initial fluid medium are provided from theneutralizing agent reservoir and the initial fluid medium reservoir,respectively. Any suitable pump may be used, but in some embodiments,for example, a pump that provides a flow of about 150 cubic centimetersper minute (cc/min) at a pressure of 240 bar is used to provide theneutralizing agent and the initial fluid medium to the extruder. Inother embodiments, a liquid injection pump provides a flow of 300 cc/minat 200 bar or 600 cc/min at 133 bar. In some embodiments, theneutralizing agent and initial fluid medium are preheated in apreheater.

The base polymer, in the form of pellets, powder, or flakes, is fed fromthe feeder to an inlet of the extruder where the base polymer is meltedor compounded. The polymeric stabilizing agent, polymeric couplingagent, and the polymeric performance improving agent can also be fedsimultaneously with the base polymer into the extruder via the feeder;or in the alternative, the polymeric stabilizing agent can be compoundedinto the base polymer, and then fed into the extruder via the feeder. Inthe alternative, the polymeric stabilizing agent can be metered via aninlet prior to the emulsification zone into the molten compoundincluding the base polymer. In some embodiments, the polymericstabilizing agent is added with the base polymer and in otherembodiments, the polymeric stabilizing agent is provided separately tothe twin screw extruder. The polymer melt is then delivered from the mixand convey zone to an emulsification zone of the extruder where theinitial amount of fluid medium and neutralizing agent from the fluidmedium and neutralizing agent reservoirs are added through an inlet. Insome embodiments, the polymeric coupling agent and the polymericperformance improving agent can be added additionally or exclusively tothe fluid medium stream.

In some embodiments, further fluid medium may be added via fluid mediuminlet from fluid medium reservoir in a dilution and cooling zone of theextruder. Typically, the dispersion is diluted to at least 30 weightpercent fluid medium in the cooling zone. In addition, the dilutedmixture may be diluted any number of times until the desired dilutionlevel is achieved. In some embodiments, the dispersion is further cooledafter exiting the extruder by the use of a suitable heat exchanger. Inother embodiments, fluid medium is not added into the twin screwextruder but rather to a stream containing the melt after the melt hasexited from the extruder. In this manner, vapor pressure (e.g., steampressure) build-up in the extruder is eliminated and the dispersion isformed in a secondary mixing device such as a rotor stator mixer.

In another embodiment, the coating composition can be formed in acontinuous high shear mixer without the use of a melt kneading extruder.In this embodiment, the first stream including one or more liquid ormolten base polymers is supplied to a continuous high shear mixer from asuitable liquid pump for example, a syringe pump, gear pump, orprogressive cavity pump. The first stream is flowed through a firstconduit and merged continuously with a second stream containing fluidmedium that is flowed through a second conduit. The first and secondstreams are merged into a disperser in the presence polymericstabilizing agent, polymeric coupling agent and the polymericperformance improving agent with the neutralizing agent. The agents canbe added to either the first or second stream, or as a separate stream.A third stream including the fluid medium (e.g., water) can be addeddownstream from the disperser. The flow rates of the streams areadjusted to achieve a dispersion having the desired amount of polymerphase and percent solids. The disperser can be any one of a number ofcontinuous inline mixers, for example, an IKA high-shear mixer, Oakesrotor stator mixer, Ross mixer, Silverson mixer, or centrifugal pump.The rotations-per-minute (rpm) setting of the disperser can be used tohelp control the particle size of the dispersed hydrophobic phase in thedispersion. The system can be heated to provide the polymer andneutralizer components at a suitable viscosity for pumping. Steamformation is reduced by controlling the pressure through the use of abackpressure regulator, gear pump, metering pump, or other suitabledevice near the exit of the process. In some embodiments, the dispersionis further cooled after exiting the disperser by the use of a suitableheat exchanger.

In another embodiment, the coating composition can be formed in a batchor semi-batch process using a high shear mixer where the mixer may, forexample, be disposed within a pressurized tank to, for example, reducesteam formation. All or at least a portion of the dispersion is removedfrom the tank during processing, and optionally cooled by the use of asuitable heat exchanger.

During the preparation of the coating composition, optionally one ormore fillers; optionally one or more additives such as catalysts,cross-linkers, wetting agents, defoamers, flow agents, release agents,slip agents, anti-blocking agents, additives to mask sulfur staining,pigment wetting/dispersion agents, anti-settling agents, UV stabilizers,adhesion promoters; optionally one or more lubricants such as fatty acidester wax, silicon-based wax, fluorine-based wax, polyethylene or anyother similar polyolefin wax, carnauba wax, lanolin wax or the like;optionally one or more corrosion inhibitors such as aluminum, and zinc:optionally one or more pigments, e.g. titanium dioxide, mica, calciumcarbonate, barium sulfate, silica, zinc oxide, milled glass, aluminumtrihydrate, talc, antimony trioxide, fly ash, and clay or the like;optionally one or more dyes; optionally one or more co-solvents, e.g.glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate,alcohols, mineral spirits, and benzoate esters or the like; optionallyone or more dispersants, e.g. aminoalcohols, and polycarboxylates;optionally one or more surfactants; optionally one or more defoamers;optionally one or more preservatives, e.g. biocides, mildewcides,fungicides, algaecides, and combinations thereof; optionally one or morethickeners, e.g. cellulosic based thickeners such as hydroxyethylcellulose, hydrophobically modified alkali soluble emulsions (HASEthickeners such as UCAR POLYPHOBE TR-116) and hydrophobically modifiedethoxylated urethane thickeners (HEUR); or optionally one or moreadditional neutralizing agents, e.g. hydroxides, amines, ammonia, andcarbonates may be added to the coating composition formulation; or inthe alternative, may be added to the dispersion post dispersionformulation process.

During the preparation of the coating composition, the polymericstabilizing agent may also be added to the dispersion post dispersionformulation process.

Optionally during the dispersion of the base polymer another polymerdispersion or emulsion may be used as a portion of the aqueous phase ofthe dispersion. Examples include, but are not limited to, acrylic,epoxy, polyester, polyurethane, polyolefin, polyamide and the likecontaining dispersions, emulsions, suspensions, colloidal suspensions.

The coating composition may be used, for example, in a metal coating, apipe coating, a coil coating, a tank liner coating, over non-ferroussubstrates (i.e., epoxy, polyurethane), or direct to a metal substrate,among others. One advantage of the coating layer of the presentdisclosure is the combination of its acid and base resistance,flexibility and its adhesion to a variety of substrate surfaces (e.g.,metal, epoxy, polyurethane, cement substrates).

Examples of such a substrate surface include, but are not limited to, ametal substrate. The metal substrate includes one or more metalsincluding, but not limited to, aluminum and aluminum alloys,electrolytic tinplate cold rolled low carbon mild steel (“ETP”),electrolytic chromium/chromium oxide coated cold rolled low carbon mildsteel (ECCS), and any other pre-treated steel. Pretreatment may include,but is not limited to, treatment with phosphoric acid, zirconiumphosphate, chromium phosphate, and the like as well as silanes forreasons such as primary corrosion protection and improved adhesion. Themetal substrate may comprise a sheet, strip or a coil.

The metal substrate may be pre-coated with one or more pre-coatingcompositions. Such pre-coating compositions may optionally furtherinclude, but are not limited to, one or more resin binders, one or moreresin crosslinkers, one or more solvents, one or more additives, and oneor more pigments. Exemplary resin binders include, but are not limitedto, epoxy, polyester, polyurethane, polyvinyl chloride containingorganosols/vinyls, phenolic, alkyd, oleoresin, acrylic resin, and thelike. Exemplary crosslinkers include, but are not limited to,phenol-formaldehyde resins; amino-formaldehyde resins including but notlimited to urea-formaldehyde, melamine formaldehyde, benzoguanamineformaldehyde, anhydride resins, blocked isocyanate resins and epoxygroups containing resins, including but not limited to, epoxy resins,epoxy groups containing polyesters, acrylic resins, vinyl resins or thelike.

Exemplary solvents and thinners include, but are not limited to, glycolethers, alcohols, aromatics, e.g. aromatic hydrocarbons, white spirit,branched ketones and esters. Exemplary additives include, but are notlimited to, catalysts, lubricants, wetting agents, defoamers, flowagents, release agents, slip agents, anti-blocking agents, additives tomask sulfur staining, pigment wetting/dispersion agents, anti-settlingagents, UV stabilizers, adhesion promoters. Pigments include, but arenot limited to titanium dioxide, zinc oxide, aluminum oxide, zinc andaluminum.

The substrate may also be pre-coated with one or more pre-coatedlaminate compositions. Such compositions may, for example, includepolyethylene, epoxy, polyurethane, polypropylene, or polyestercompositions, and may be applied either as a film via film laminationprocess or melt-extrusion coating process onto the metal surface.

In addition to metal substrates, the coating composition of the presentdisclosure can also be used on polymer surfaces (e.g., polyurethane,cured epoxy), cement surfaces, cellulose based surfaces, mineral basedsurfaces and/or ceramic surfaces and combinations thereof, among others.

The individual coating layer may be applied via a variety of methods;for example, via roller coating, spray coating, powder coating, dipcoating, electrodeposition coating, printing, wash coating, flowcoating, curtain coating. The thicknesses of the resulting coating layercan range from 0.01 micrometer (μm) to 250 μm. All individual values andsub-ranges from 0.01 μm to 250 μm are included herein and disclosedherein; for example, the thickness of the coating layer can be from alower limit of 0.01 μm, 0.02 μm or 0.03 μm to an upper limit of 150 μm,200 μm or 250 μm. For example, the coating composition may comprise from0.01 μm to 150 μm, or from 0.01 μm to 200 μm, or from 0.01 μm to 250 μm,or from 0.02 μm to 150 μm, or from 0.02 μm to 200 μm, or from 0.02 μm to250 μm, or from 0.03 μm to 150 μm, or from 0.03 μm to 200 μm or from0.03 μm to 250 μm. One or more coating layers may be applied to asubstrate.

The coating composition applied to the at least one surface of the metalsubstrate may be dried via a conventional drying method to form thecoating layer. Such a conventional drying method includes but, is notlimited to, air drying, convection oven drying, hot air drying, and/orinfrared oven drying. The coating composition applied to the at leastone surface of the metal substrate may be dried, for example, at atemperature in the range of equal or greater than the melting pointtemperature of the base polymer; or in the alternative, it may be driedat a temperature in the range of less than the melting point of the basepolymer.

The coating composition applied to the at least one surface of the metalsubstrate may be dried at a temperature in the range of 100° C. to 230°C. for less than about 40 minutes, for example, less than 20 minutes, orless than 10 minutes, or less than 5 minutes, or less than 2 minutes, orless than 1 minute or less than 20 seconds. All individual values andsubranges from 100° C. to 230° C. are included herein and disclosedherein; for example, the coating composition applied to the at least onesurface of the metal substrate may be dried at a temperature in therange of 120° C. to 210° C. for less than about 40 minutes, for example,less than 20 minutes, or less than 10 minutes, or less than 5 minutes,or less than 2 minutes, or less than 1 minute, or in the alternative,the coating composition applied to the at least one surface of the metalsubstrate may be dried at a temperature in the range of 140° C. to 200°C. for a period of less than about 40 minutes, for example, less than 20minutes, or less than 10 minutes, or less than 5 minutes, or less than 2minutes, or less than 1 minute.

The temperature of the coating composition applied to the at least onesurface of the metal substrate may be raised to a temperature in therange of equal or greater than the melting point temperature of the basepolymer for a period of less than about 40 minutes. All individualvalues and subranges from less than about 40 minutes are included hereinand disclosed herein; for example, the temperature of the coatingcomposition applied to the at least one surface of the metal substratemay be raised to a temperature in the range of equal or greater than themelting point temperature of the base polymer for a period of less thanabout 20 minutes, or in the alternative, the temperature of the coatingcomposition applied to the at least one surface of the metal substratemay be raised to a temperature in the range of equal or greater than themelting point temperature of the base polymer for a period of less thanabout 5 minutes, or in another alternative, the temperature of thecoating composition applied to the at least one surface of the metalsubstrate may be raised to a temperature in the range of equal orgreater than the melting point temperature of the base polymer for aperiod in the range of about 0.5 to 300 seconds. In another alternative,the temperature of the coating composition applied to the at least onesurface of the metal substrate may be raised to a temperature in therange of less than the melting point temperature of the base polymer fora period of less than 40 minutes. All individual values and subrangesfrom less than about 40 minutes are included herein and disclosedherein; for example, the temperature of the coating composition appliedto the at least one surface of the metal substrate may be raised to atemperature in the range of less than the melting point temperature ofthe base polymer for a period of less than about 20 minutes, or in thealternative, the temperature of the coating composition applied to theat least one surface of the metal substrate may be raised to atemperature in the range of less than the melting point temperature ofthe base polymer for a period of less than about 5 minutes, or inanother alternative, the temperature of the coating composition appliedto the at least one surface of the metal substrate may be raised to atemperature in the range of less than the melting point temperature ofthe base polymer for a period in the range of about 0.5 to 300 seconds.

EXAMPLES

The following examples illustrate the present disclosure but are notintended to limit the scope of the disclosure. The examples of theinstant disclosure demonstrate that the coating composition applied toat least one surface of a metal substrate provide for improved coatinglayer flexibility as well as coating layer adhesion to the metalsubstrate.

Preparation and Curing of Coatings Layers

Prepare coating layers on uncoated cold rolled steel or iron phosphatedsteel substrates (Q-Lab Corporation and ACT Test Panel Technologies)using a drawdown bar with a 10 mil gap (equal to 0.0254 millimeters(mm)). Cure all coatings compositions at 140° C. for 10 minutes, exceptfor Inventive Example 5 and Example 6 and Comparative Example A, whichwere cured at 200° C. for 10 minutes, and Comparative Examples G and Hwhich cure for 7 days at room temperature (23° C.). Thicknesses of thecoating layers ranged from 1.9-5.8 mil.

Prepare coating layers from the coating compositions of Examples 1-5 onpolyurethane, thermoplastic olefin (TPO), epoxy, and fiber/cementsubstrates to test adhesion. Cast films of the coating composition usinga 10 mil gap bar. Prepare polyurethane substrates by applying a wet filmof POLANE™B polyurethane enamel blended with V66V27 catalyst, availablefrom Sherwin Williams, using a 10 mil gap bar on cold rolled steelpanels and cure the panels overnight at room temperature (23° C.)followed by force curing at 80° C. for 40 minutes.

Epoxy substrates were e-coated panels available from ACT Test PanelTechnologies. TPO substrates are available from Custom Precision R&DTesting Panels, Inc. 30 cm×60 cm×3-4 mm fiber/cement panels consistingof water/cement/cellulose/textile fibers/amorphous silica/calciumcarbonate substrates are available from the Etex Group.

Thickness Measurement

Thickness of the coating layer was measured by according to ASTM-D1186-93, a non-destructive measurement of dry film thickness ofnon-magnetic coatings applied to a ferrous base, using a Positector™6000 coating thickness gauge. The standard panel without any coating wasused for calibration. The thickness of the coating layer on the coatedpanels was the average of a minimum of 4 measurements. The measuredthickness was reported in mils (25 microns/mil).

Adhesion

Test cross-hatch adhesion according to ASTM-D 3359-08. Make a squarelattice pattern with 10 cuts in each direction with 1 mm distancebetween neighboring cuts. Apply a pressure sensitive tape over the cutarea and pull the tape parallel to the substrate surface. Evaluate theadhesion using a scale from 0B to 5B, with 5B indicating perfectadhesion to the substrate and 0B indicating that there was completeremoval of the coating from the substrate.

5B The edges of the cuts are completely smooth; none of the squares ofthe lattice is detached. 4B Small flakes of the coating are detached atintersections; less than 5% of the area is affected. 3B Small flakes ofthe coating are detached along the edges and at intersections of cuts.The area affected is 5-15% of the lattice. 2B The coating has flakedalong the edges and on parts of the squares. The area affected is 15-35%of the lattice. 1B The coating has flaked along the edges of cuts inlarge ribbons and whole squares have detached. The area affected is35-65% of the lattice. 0B Flaking and detachment is worse than 1B

Particle Size Measurement

Measure particle size using a Coulter LS-230 or Coulter LS-13-320particle size analyzer (Beckman Coulter Corporation).

Measurement Percent Solids

Measure percent solid using a microwave solids analyzer or an infraredsolids analyzer.

Acid/Base Resistance

Test the coating layer resistance to 98% (mass fraction) sulfuric acid,37% (kg HCl/kg) hydrochloric acid, glacial acetic acid (12 Normality)and 50% (kg NaOH/kg) sodium hydroxide. Place drops of each of the acids,or base, on the coating surface and place a plastic cap over theacid/base to inhibit evaporation. Add acid or base, as needed, tomaintain exposure of the coating. Keep the samples at room temperature(23° C.) for 7 days and then completely rinse with water. After thesamples dry, test adhesion and rate from 1 to 5, with 5 indicating anintact coating and 1 indicating a completely etched coating based onadhesion of the coating after exposure.

Freeze/Thaw Durability

Measure the tolerance of the coatings to temperature fluctuation bymeasuring their adhesion to the substrates after cycles of heating andcooling treatment. One cycle is heating in oven at 50° C. for 30 minfollowed by immersion in dry ice (solid carbon dioxide, −78.5° C. atatmospheric pressure) for 30 minutes. Measure adhesion according to thecrosshatch adhesion procedure, as described herein, after 5 and 10cycles of freeze/thaw treatment.

Solvent Resistance (MEK Double Rub)

Test solvent resistance according to ASTM D4752 using Methyl EthylKetone (MEK). Test samples using a piece of cotton cheesecloth attachedwith copper wire to a 1.5 pound hammer. Saturate the cheesecloth withMEK and place on the coating. Push the hammer forward and then back at arate of approximately 1 second per cycle. Visually inspect the coatinglayer after every 20 double rub cycle for any signs of damage ordelaminating. Repeat this procedure until a bare panel is showing(record this as the MEK DR result for the sample) or after reaching 200double rubs in total. Alternatively, an automated tester, available fromDJH Designs may be used. The automated tester works in a semi-automaticfashion by moving a cotton pad, attached to a weighted block thatapplies about 2.2 lb/in², in a back and forth motion across the coatedpanel. Each back and forth is referred to as one double rub.

Impact Resistance

Measure impact resistance of the coating layer using a Gardner fallingweight impact tester according to ASTM D-2794. Measure indentation inboth direct and indirect modes. Units of measure are inch-lbs.

Mandrel Wedge Bend

Test mandrel wedge bend flexibility of the coating layer using a conicalmandrel following ASTM D522-93a. Measurements are in millimeters fromthe small end of the mandrel to where cracking has ceased.

EXAMPLES Example 1

Prepare Example 1 according to the following procedures based on theformulation components listed in Table I. For the base polymer useVERSIFY™ DP-4000.01 (The Dow Chemical Company, CAS No. 9010-79-1), whichis a propylene/ethylene copolymer having a melt index of approximately21-29 g/10 min (ASTM D1238, 230° C./2.16 Kg); for a polymeric couplingagent use LICOCENE™ 6452 (CLARIANT, CAS 25722-45-6), which is apropylene-maleic anhydride graft copolymer with an acid value of about41; and for a polymeric stabilizing agent use PRIMACOR™ 5980i (The DowChemical Company, CAS No. 9010-77-9), which is an ethylene acrylic-acidcopolymer having an acrylic acid content in the range of 19.5-21.5weight percent and a melt index of approximately 300 g/10 min (ASTMD1238, 190° C./2.16 Kg).

Feed the base polymer, the polymeric coupling agent and the polymericstabilizing agent into a 25 mm twin screw extruder (extruder speedapproximately 500 rotations-per-minute (rpm)) by means of controlledrate feeders to be forwarded and melted. Ramp the extruder temperatureprofile to approximately 150° C., prior to the introduction of initialwater and N,N-dimethylethanolamine (DMEA, 100%) (the neutralizing agent,CAS Number 108-01-0). Mix the DMEA and the water together and fed to theextruder at the initial water introduction point. Feed the dilutionwater via a second pump into the dilution zone of the extruder. Theinitial water and dilution water were optionally pre-heated toapproximately 140° C. Use a back-pressure regulator at the extruderoutlet to adjust to a suitable pressure inside the extruder barrel toreduce steam formation at the operating temperature. Cool the resultingcoating composition and filter through a 200 micron filter.

Example 2

Prepare Example 2 according to the following procedures based on theformulation components listed in Table I. For a first base polymer useDMDA-8940 HDPE (The Dow Chemical Company, CAS No. 9002-88-4), which is ahigh density polyethylene polymer having a melt index of approximately40-48 g/10 min (ASTM 1238, 190° C./2.16 kg); for a polymeric performanceimproving agent use AMPLIFY GR-204, which is an ethylene-maleicanhydride graft copolymer with a melt index of approximately 9-15 g/10min (ASTM 1238, 190° C./2.16 kg) and a maleic anhydride level ofapproximately 1-1.4 weight percent; for a polymeric coupling agent useLICOCENE™ 4351 (CLARIANT); and for a polymeric stabilizing agent usePRIMACOR™ 5980i (The Dow Chemical Company, CAS No. 9010-77-9).

Feed each of the base polymer, the polymeric performance improvingagent, the polymeric coupling agent and the polymeric stabilizing agentinto a 25 mm twin screw extruder by means of controlled rate feeders tobe forwarded and melted. The remainder of the process is as describedfor Example 1.

Example 3

Example 3 was prepared according to the following procedures based onthe formulation components listed in Table I. For a first base polymeruse DMDA-8940 HDPE (The Dow Chemical Company, CAS No. 9002-88-4); for apolymeric performance improving agent use AMPLIFY GR-204; as a polymericcoupling agent LICOCENE™ 4351 (CLARIANT, CAS No. 9006-26-2); and as apolymeric stabilizing agent use PRIMACOR™ 5980i (The Dow ChemicalCompany, CAS No. 9010-77-9).

Feed each of the base polymer, the polymeric performance improvingagent, the polymeric coupling agent and the polymeric stabilizing agentinto a 25 mm twin screw extruder by means of controlled rate feeders tobe forwarded and melted. The remainder of the process is as describedfor Example 1.

Example 4

Example 4 was prepared according to the following procedures based onthe formulation components listed in Table I. For a base polymer useDMDA-8940 HDPE (The Dow Chemical Company, CAS No. 9002-88-4); for apolymeric coupling agent use AC575-P, which is an ethylene maleicanhydride Copolymer (HONEYWELL INTERNATIONAL. INC., CAS No. 9006-26-2)having an acid value of approximately 35; and for a polymericstabilizing agent use PRIMACOR™ 5980i (The Dow Chemical Company, CAS No.9010-77-9).

Feed each of the base polymer, the polymeric coupling agent and thepolymeric stabilizing agent into a 25 mm twin screw extruder by means ofcontrolled rate feeders to be forwarded and melted. The remainder of theprocess is as described for Example 1.

Example 5

Example 5 was prepared according to the following procedures based onthe formulation components listed in Table I. For a base polymer use6D43 Polypropylene (Braskem, CAS No. 9002-88-4), which is apolypropylene polymer having a melt index of approximately 35 g/10 min(ASTM 1238, 230° C./2.16 kg); for a polymeric coupling agent useLICOCENE™ 6452 (CLARIANT, CAS 25722-45-6); and for a polymericstabilizing agent use PR1MACOR™ 5980i (The Dow Chemical Company, CAS No.9010-77-9).

Feed each of the base polymer, the polymeric coupling agent and thepolymeric stabilizing agent into a 25 mm twin screw extruder by means ofcontrolled rate feeders to be forwarded and melted. The remainder of theprocess is as described for Example 1, except ramp the extrudertemperature profile to approximately 170° C., prior to the introductionof initial water and DMEA (100%) (CAS Number 108-01-0) as theneutralizing agent.

Example 6

Example 6 was prepared according to the following procedures based onthe formulation components listed in Table I. For the base polymer use6D43 Polypropylene (Braskem, CAS No. 9002-88-4); for the polymericperformance improving agent use VERSIFY™4200, available from the DowChemical Company (CAS No. 9010-79-1); for the polymeric coupling agentuse LICOCENE™ 6452 (CAS 25722-45-6); and as the polymeric stabilizingagent use PRIMACOR™ 5980i (CAS No. 9010-77-9).

Feed each of the base polymer, the polymeric performance improvingagent, the polymeric coupling agent and the polymeric stabilizing agentinto a 25 mm twin screw extruder (speed approximately 1200 rpm) by meansof controlled rate feeders to be forwarded and melted. The initial waterand dilution water were optionally pre-heated to approximately 150° C.The remainder of the process is as described for Example 1.

Comparative Example A

Comparative Example A was prepared according to the following proceduresbased on the formulation components listed in Table I. For the basepolymer use 6D43 Polypropylene (Braskem, CAS No. 9002-88-4), which is apolypropylene polymer having a melt index of approximately 35 g/10 min(ASTM 1238, 230° C./2.16 kg); for the polymeric stabilizing agent usePRIMACOR™ 5980i (The Dow Chemical Company, CAS No. 9010-77-9).

Feed each of the base polymer and the polymeric stabilizing agent into a25 mm twin screw extruder (extruder speed approximately 500 rpms) bymeans of controlled rate feeders to be forwarded and melted. Ramp theextruder temperature profile to approximately 150° C., prior to theintroduction of initial water and DMEA (100%) (CAS Number 108-01-0) asthe neutralizing agent at the initial water introduction point. Feeddilution water via a second pump into the dilution zone of the extruder.The initial water and dilution water were optionally pre-heated toapproximately 150° C. Use a back-pressure regulator at the extruderoutlet to adjust the pressure inside the extruder barrel to reduce steamformation at the operating temperature. Cool the content of the 25 mmtwin screw extruder to a temperature below 100° C. by the end of theextruder after adding the dilution water.

Comparative Example B

Prepare Comparative Example B according to the following proceduresbased on the formulation components listed in Table I. For the basepolymer use ENGAGE™ 8407 (The Dow Chemical Company, CAS No. 26221-73-8),which is an ethylene-octene copolymer having a melt index ofapproximately 22-38 g/10 min (ASTM 1238, 190° C./2.16 kg); for thepolymeric stabilizing agent use PRIMACOR™ 5980i (The Dow ChemicalCompany, CAS No. 9010-77-9).

Feed each of the base polymer and the polymeric stabilizing agent into a25 mm twin screw extruder (extruder speed approximately 500 rpm) bymeans of controlled rate feeders to be forwarded and melted. Ramp theextruder temperature profile to approximately 130° C., prior to theintroduction of initial water and DMEA (100%) (CAS Number 108-01-0) asthe neutralizing agent at the initial water introduction point. Cool thecontent of the 25 mm twin screw extruder to a temperature below 100° C.by the end of the extruder after adding the dilution water.

Mix the DMEA and the water together and fed to the extruder at theinitial water introduction point. Feed the dilution water via a secondpump into the dilution zone of the extruder. The initial water anddilution water were not pre-heated. Use a back-pressure regulator at theextruder outlet to adjust to a suitable pressure inside the extruderbarrel to reduce steam formation at the operating temperature. Cool theresulting dispersions and filter through a 200 micron filter.

Comparative Example C

Comparative Example C was prepared according to the following proceduresbased on the formulation components listed in Table I. For the basepolymer use YERSIFY™ 3200 (The Dow Chemical Company, CAS No. 9010-79-1,which is a propylene/ethylene co-polymer having a melt index ofapproximately 6-10 g/10 min (ASTM 1238, 230° C./2.16 kg); for apolymeric coupling agent use LICOCENE™ 6452 (CLARIANT, CAS 25722-45-6)and for a polymeric stabilizing agent use PRIMACOR™ 5980i (The DowChemical Company, CAS No. 9010-77-9).

Feed each of the base polymer, the polymeric coupling agent and thepolymeric stabilizing agent into a 25 mm twin screw extruder (extruderspeed approximately 470 rpms) by means of controlled rate feeders to beforwarded and melted. Ramp the extruder temperature profile toapproximately 150° C., prior to the introduction of initial water andDMEA (100° A) (CAS Number 108-01-0) as the neutralizing agent at theinitial water introduction point. Feed dilution water via a second pumpinto the dilution zone of the extruder. The initial water and dilutionwater were optionally pre-heated to approximately 140° C. After addingdilution water, cool the mixture to a temperature below 100° C. by theend of the extruder. At the extruder outlet, a back-pressure regulatorwas used to adjust to a suitable pressure inside the extruder barrel toreduce steam formation at the operating temperature. The resultingdispersions were cooled and filtered through a 200 micron filter.

Comparative Example D

Comparative Example D was prepared according to the following proceduresbased on the formulation components listed in Table I. For the basepolymer use INFUSE™ 9807 (The Dow Chemical Company, CAS No. 26221-73-8),which is an olefin block copolymer having a melt index of approximately12-18 g/10 min (ASTM 1238, 190° C./2.16 kg); and for a non-polymericstabilizing agent use Behenic acid (a surfactant, 100% active).

Feed each of the base polymer and the non-polymeric stabilizing agentinto a 25 mm twin screw extruder (extruder speed approximately 500 rpms)by means of controlled rate feeders to be forwarded and melted. Ramp theextruder temperature profile to approximately 140° C., prior to theintroduction of initial water and potassium hydroxide (KOH, 30 wt % inwater) (CAS Number 71769-53-4) as the neutralizing agent at the initialwater introduction point. Feed dilution water via a second pump into thedilution zone of the extruder. The initial water and dilution water wereoptionally pre-heated to approximately 120° C. At the extruder outlet, aback-pressure regulator was used to adjust to a suitable pressure insidethe extruder barrel to reduce steam formation at the operatingtemperature. The resulting dispersions were cooled and filtered througha 200 micron filter.

Comparative Example E

Comparative Example E was prepared according to the following proceduresbased on the formulation components listed in Table I. For the basepolymer use AMPLIFY™ EA103 (The Dow Chemical Company, CAS 26221-73-8) isan ethylene-ethyl acrylate copolymer having a melt index ofapproximately 18-24 g/10 min (ASTM 1238, 190° C./2.16 kg); and for thepolymeric stabilizing agent use PRIMACOR™ 5980i (The Dow ChemicalCompany, CAS No. 9010-77-9).

Feed each of the base polymer and the polymeric stabilizing agent into a25 mm twin screw extruder (extruder speed approximately 470 rpms) bymeans of controlled rate feeders to be forwarded and melted. Ramp theextruder temperature profile to approximately 160° C., prior to theintroduction of initial water and N,N-dimethylethanolamine (100%) (CASNumber 108-01-0) as the neutralizing agent at the initial waterintroduction point. The initial water and dilution water were optionallypre-heated to approximately 140° C. After adding dilution water, coolthe mixture to a temperature below 100° C. by the end of the extruder.At the extruder outlet, a back-pressure regulator was used to adjust toa suitable pressure inside the extruder barrel to reduce steam formationat the operating temperature. The resulting dispersions were cooled andfiltered through a 200 micron filter.

Comparative Example F

Comparative Example F was prepared according to the following proceduresbased on the formulation of components listed in Table 2. For the basepolymer use OudraSperse™ WB 4001 (The Dow Chemical Company), which is awaterborne novolac epoxy dispersion with approximately 57-59 weightpercent solids and an epoxy equivalent weight of approximately 184-204,and OudraCure WB 8001 Curing Agent (The Dow Chemical Company), which isa polyamine adduct with approximately 50 weight percent solids and anamine hydrogen equivalent weight of 300 (as delivered). These twocomponents were blended using a high speed mixer at approximately 2000rpms.

Comparative Example G

Comparative Example G was prepared according to the following proceduresbased on the formulation of components listed in Table 2. For the basepolymer use D.E.N™ 438 (The Dow Chemical Company), which is a novolacepoxy resin with an epoxy equivalent weight of approximately 184-204 andblended with xylene (CAS No. 1330-20-7) as a solvent. Add POLYPDX 1H7016(The Dow Chemical Company), which is a phenol free modified Mannich basecuring agent with an amine hydrogen equivalent weight of 70 (asdelivered), to the D.E.N™ 438/xylene mixture and blended using a highspeed mixer at approximately 2000 rpms.

TABLE 1 Poly Perfor Poly Polymeric Neutral- Initial Dilution AverageBase Improv- Coup stabilizing izing Water Water Particle Polymer AgentAgent agent Agent Rate Rate Size (g/min) (g/min) (g/min) (g/min) (mL/(mL/ (mL/ Diameter Wt % Ex (wt. %) (wt. %) (wt. %) (wt. %) min) min)min) (μm) Solids 1 VERS (0) LICOC PRIM 5980i DMEA 19.1 83 0.77 46.94000.01  6542 (17.0)  (6.4) (52.9)     (5.67) (22.5) (70)      (7.5) 2DMDA- AMPLIFY LICOC PRIM 5980i DMEA 60.5 360 0.56 45.5 8940    GR-2044351 (42.4) (31.9) (192.5)   (40.3)    (27.5) (14)   (616)    (13.3)   (9.1) 3 DMDA- AMPLIFY LICOC PRIM 5980i DMEA 66.6 360 0.77 47.98940    GR-204 4351 (66.6) (33.2) (175.5)   (39.3)    (21.2) (22)  (58)   (13)    (7) 4 DMDA- (0) Honey PRIM 5980i DMEA 15.1 85 1.1 45.08940    AC575-P (15.1)  (5.6) (53)      (7.6) (20)   (70)    (10) 5 6D43(0) LICOC PRIM 5980i DMEA 70 320 1.0 42.0 (212)   6542 (68)   (26)  (70)    (23) (22.4)    (7.6) 6 6D43 VERSIFY LICOC PRIM 5980i DMEA 73 2560.95 45.0 (182)   4200   6542 (68)   (41)   (60)   (30)   (23) (22.4)(10)     (7.6) Comp 6D43 (0)   (0) PRIM 5890i DMEA 20.0 85 2.49 40.8 A(52.9) (22.7)  (6.07) Comp ENGAG (0)   (0) PRIM 5980i DMEA 15.1 75 0.7245.2 B E 8407 (11.3)  (3.92) (64.3) Comp VERS (0) LICOC PRIM 5980i DMEA16.4 83 1.3 49.0 C 3200    6542 (17.0)  (6.42) (52.9)     (5.67) CompInfuse (0)   (0) Behenic KOH 2.7 86 1.1 46.2 D D9807 Acid (1)  (75.6) (2.3) Comp Amplify (0)   (0) PRIM 5980i DMEA 10.9 70 2.8 52.5 E EA103(15.1)  (5.2) (60.5)

TABLE 2 Table of Comparative Epoxy Coatings Base Polymer Curing agentSolvent (Wt %) (Wt %) (Wt %) Comp F OUDRASPERSE 4001 OUDRACURE 8001(52.7) (47.3) Comp G DEN 438 Polypox IH7016 Xylene (60.7) (24.1) (15.2)

TABLE 3 Performance Results for Examples 1-6 and Comparative ExamplesA-G on Uncoated Cold Rolled Steel Chemical Resistance Film MEK 7 Day 7Day 10 Cycle Mandrel Thickness Direct Reversed Double 7 Day 7 Day Acetic50% F/T Wedge Sample (mil) Adhesion Impact Impact Rubs H₂SO₄ HCl AcidNaOH Adhesion Bend (mm) 1 2.8 5B 60 100 80 4 5 5 5 4 0 2 2.6 5B 14060 >200 5 5 5 5 5 35 3 2.7 5B 160 120 200 0 5 4 5 5 50 4 2.7 5B 8040 >200 4 5 4 5 4 38 5 3.0 4B 0 0 200 1 0 3 5 5 50 6 1.6 5B 160 40 >2000 0 0 — — 0 A 2.5 2B 0 0 160 5 3 5 5 2 0 B 2.4 0B 0 0 200 0 0 0 0 5 80 C2.9 2B 120 120 92 0 5 0 5 5 0 D 1.0 0B 40 80 15 0 0 0 0 0 0 E 3.0 2B 020 200 0 1 3 5 5 0 F 3.3 5B 20 0 >200 5 5 3 5 5 90 G 5.8 5B 20 20 >200 55 3 5 3 90

TABLE 4 Coating Adhesion to Substrates Coating Composition Cold RolledSteel Polyurethane Epoxy Cement Example 1 5B 4B 5B 5B Example 2 5B 4B 5B0B Example 3 5B 5B 5B 3B Example 4 4B 4B 5B 5B Example 5 4B 5B 5B 5BComp Ex A 2B 0B 5B 3B Comp Ex B 5B 0B 5B 3B Comp Ex C 0B 0B 0B 5B CompEx D 0B 0B 0B 0B Comp Ex E 2B 0B 0B 5B

TABLE 5 Adhesion, Impact Resistance, and Flexibility for CoatingCompositions (200° C. Cure Temperature) on Polyurethane and EpoxySubstrates Direct Reversed Mandrel Impact Impact Wedge Bend Adhesion(inch-lb) (inch-lb) (mm) Epoxy Substrate Example 1 5B 60 160 0 Example 25B 160 120 0 Example 3 5B 160 120 0 Example 5 5B 120 20 0 PolyurethaneSubstrate Example 1 5B 100 40 0 Example 2 5B 160 100 0 Example 3 5B 160120 0 Example 5 4B 40 0 0

TABLE 6 Performance Properties of Examples with the Addition of PrimidCross-linker (0.6 wt. % of Primid QM-1260 was added to the dispersionand mixed for 3 minutes at 3000 rpms). Direct Reverse Mandrel FilmImpact Impact 7 Day 7 Day 7 Day Wedge Thick (inch- (inch- Acetic 7 DaySulfuric 50% Bend Sample (mils) MEK lbs) lbs) Adhesion Acid HCl AcidNaOH (mm) Ex 1 2.9 180 160 160 5B 0B 5B 0B 5B 80 Ex 2 1.6 200 160 160 5B5B 3B 5B 58 0 Ex 3 1.8 200 140 120 5B 5B 5B 5B 5B 0 Ex 4 1.7 200 140 1205B 58 5B 3B 5B 40 Ex 5 3.2 200 160 160 5B 58 58 5B 5B 0 Ex 6 3.0 200 160160 5B 5B 5B 5B 5B — Comp 1.6 200 0 0 0B 0B 0B 0B 5B 0 Ex A Comp 2.4 127160 160 5B 5B 1B 0B 5B 0 Ex B Comp 1.5 120 0 0 3B 1B 0B 3B 1B 80 Ex CComp 1.4 25 60 0 0B 08 0B 0B 0B 0 Ex D Comp 2.1 200 0 0 5B 4B 0B 0B 5B 0Ex E Comp 1.2 150 0 0 0B 0B 0B 0B 0B 0 Ex F

1. A coating composition, comprising: 40 to 80 weight percent (wt. %) ofa base polymer; 5 to 15 wt. % of a polymeric coupling agent; 10 to 30wt. % of a polymeric stabilizing agent; 5 to 35 wt. % of a polymericperformance improving agent; a neutralizing agent that partially orfully neutralizes the polymeric stabilizing agent; and a fluid medium,where the percent values are based on the total weight of the basepolymer, the polymeric coupling agent, the polymeric stabilizing agent,the polymeric performance improving agent of the coating composition andsum to a value of 100 wt. %.
 2. The coating composition of claim 1,where the base polymer is selected from the group consisting of anon-functionalized ethylene polymer, a non-functionalized propylenepolymer, a non-functionalized propylene/ethylene copolymer, and acombination thereof.
 3. The coating composition of claim 2, where thenon-functionalized ethylene polymer is selected from the groupconsisting of polyethylene, a polyethylene-copolymer and a combinationthereof.
 4. The coating composition of claim 2, where thenon-functionalized ethylene polymer, non-functionalized propylenepolymer, or non-functionalized ethylene/propylene copolymer has acrystalline melting point of 100° C. to 230° C.
 5. The coatingcomposition of claim 1, where the base polymer is a non-functionalizedpropylene polymer.
 6. The coating composition of claim 1, where thepolymeric stabilizing agent is an ethylene-acrylic acid andethylene-methacrylic acid copolymer having a functionality in a range of10 wt. % to 25 wt. %.
 7. The coating composition of claim 1, where thepolymeric coupling agent is selected from the group consisting of afunctionalized polypropylene, a functionalized polyethylene homopolymer,a copolymer that has been modified with carboxylic acid groups, acopolymer that has been modified with anhydride groups and a combinationthereof.
 8. The coating composition of claim 1, where the polymericperformance improving agent is selected from the group consisting offunctionalized polyethylene, functionalized polypropylene,non-functionalized copolymer of ethylene and propylene and a combinationthereof.
 9. The coating composition of claim 1, where acid groups of thepolymeric stabilizing agent are neutralized with the neutralizing agent.10. The coating composition of claim 1, where the neutralizing agent isa volatile base.
 11. The coating composition of claim 10, where thevolatile base is N,N-dimethylethanolamine.
 12. The coating compositionof claim 1, where the fluid medium is water.
 13. A coating layer formedwith the coating composition of claim
 1. 14. The coating layer of claim13, where the coating layer is on a substrate.
 15. The coating layer ofclaim 14, where the substrate is selected from the group consisting of ametal, a polyurethane, a cured epoxy, a cement or a combination thereof.16. (canceled)
 17. The coating composition of claim 1, where the coatingcomposition further includes a lubricant.
 18. The coating composition ofclaim 17, where the lubricant is a wax.
 19. The coating composition ofclaim 18, where the wax is selected from the group consisting of fattyacid ester wax, silicon-based wax, fluorine-based wax, polyolefin wax,carnauba wax, lanolin wax and combinations thereof.
 20. The coatingcomposition of claim 1, further including 0.5 to 50 wt. % of across-linking agent, where the percent values are based on the totalweight of the base polymer, the polymeric coupling agent, the polymericstabilizing agent, the polymeric performance improving agent, and thecross-linking agent of the coating composition and sum to a value of 100wt. %.
 21. The coating composition of claim 20, where the cross-linkingagent is a hydroxyalkyl amide and the coating composition includes 0.5to 10 wt. % of the cross-linking agent.